CN1123631C - Technological process of treating infertor heavy and residual oil - Google Patents
Technological process of treating infertor heavy and residual oil Download PDFInfo
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- CN1123631C CN1123631C CN 00123222 CN00123222A CN1123631C CN 1123631 C CN1123631 C CN 1123631C CN 00123222 CN00123222 CN 00123222 CN 00123222 A CN00123222 A CN 00123222A CN 1123631 C CN1123631 C CN 1123631C
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Abstract
The present invention discloses a multistage hydrocracking technical process for a suspension bed for processing poor-quality heavy oil and residual oil. After viscous crude oil or atmospheric vacuum residual oil obtained by distillation and hydrogenation catalysts are uniformly mixed, the viscous crude oil or the atmospheric vacuum residual oil obtained by distillation and the hydrogenation catalysts enter a multistage hydrocracking reaction apparatus of the suspension bed to carry out cracking hydrogenation reaction so that low-boiling point products are generated when high-pressure hydrogen (6 to 18MPa) exists. The multistage reaction apparatus used by the hydrogenation reaction of the suspension bed comprises at least a section of high-temperature reaction zone and a section of low-temperature reaction zone.
Description
The present invention relates to a kind of processing method of handling inferior heavy, residual oil, particularly a kind of floating bed hydrocracking technological process of processing inferior heavy, residual oil.
The weight that the present invention relates to, residual oil can be the residual oils that crude distillation obtains, heavy-gravity heavy crude oil, the also organism that obtains of oil sands bitumen, shale oil and the dry distillation of coal.
Along with the increase to the light-end products demand of the minimizing of light crude and market, the former oil require of some inferior heavy is used.Conversion heavy simultaneously, residual oil also comes into one's own day by day, and main purpose heavy, that residual oil transforms is the light-end products that obtain having higher-value to greatest extent the heavier feedstocks oil of the residue that obtains from petroleum distillation or other low value.
Suspension bed residual oil hydrogenation is one of important means of heavy residual oil lighting, early stage suspension bed hydrogenation process adopts solid powder th-1 catalyst more, under High Temperature High Pressure, react, thereby cause tail oil solid content height, bring certain difficulty to the following process device.The one or more reactors in series of the many employings of existing suspension bed technology, reactor is operation at high temperature all, is unfavorable for effectively carrying out of hydrogenation reaction, thereby causes the productive rate of coke higher, influences the long-term stability running of device.
Propose in the United States Patent (USP) 4923838 iron cpd (mainly being ferrous sulfate) and coal dust are ground in oil, make a kind of iron-coal paste shape catalyzer, mix with heavy oil then and carry out floating bed hydrogenation.When reaction conditions is: 438 ℃ of temperature, pressure 13.6MPa, liquid hourly space velocity is 0.55h
-1, 524 ℃
+Bottoms conversion is 61.6w%.Because the hydrogenation activity of iron catalyst is very low, must add a large amount of catalyzer in the reaction process, account for 0.5～3w% of inlet amount usually.These catalyzer all are enriched in the tail oil at last, and this tail oil that contains a large amount of solid catalyst particles is handled and utilized all very difficult.
Adopt oil soluble Fe (CO) in the United States Patent (USP) 5578197
5With the 2 ethyl hexanoic acid molybdenum be catalyzer, to contain 70w%525 ℃
+It is raw material that the cold air lake of component subtracts slag, catalyzer add-on 300 μ g/g, and reaction pressure 13.6MPa, 450 ℃ of temperature of reaction are reacted on continuous apparatus, 525 ℃
+Bottoms conversion is 68.4w%, reacts 160 hours post-reactors and stops up.Though this technological process has overcome the problem of using solid powder th-1 catalyst to exist, but owing to adopt the single hop pyroreaction, the rapid cracking of macromole in the raw material, form intermediate phase, high temperature is unfavorable for the carrying out of hydrogenation reaction, thereby makes the intermediate phase that forms have little time hydrogenation, and condensation generates coke or coke precursors, influence the long-term stability running of device, also influence the further raising of transformation efficiency.
Purpose of the present invention is exactly the shortcoming that overcomes the existing easy coking of technology, a kind of multistage suspension bed complete processing is provided, this technology can be given full play to hydrogenation and the cracked technological advantage that suspension bed possesses when processing inferior heavy, residual oil, obtain liquid oil to greatest extent and produce coke as far as possible less.
The present invention includes the following aspects: at first hydrogenation catalyst is dispersed in the stock oil, the total add-on of catalyst metal is 50～400ug.g
-1Contain and enter multistage suspension bed hydroprocessing reactor after the stock oil of catalyzer and hydrogen mix.Hydrogenation and scission reaction take place in heavy residual oil in reactor, change into low boiler cut to greatest extent.
The multistage suspension bed hydroprocessing reactor that the present invention relates to comprises at least one pyroreaction section and a low-temp reaction section.Restricted condition is positioned at for the pyroreaction section before the low-temp reaction section, and pyroreaction section and low-temp reaction section are interspersed.
Wherein the processing condition of pyroreaction section are: reaction pressure is 6～18MPa, better is 12～16MPa; Temperature of reaction is 400～500 ℃, better is 430～450 ℃; Liquid hourly space velocity is 0.2～4.0h
-1, be preferably 1～2h
-1Hydrogen to oil volume ratio (under the standard pressure) is 100～1200, better is 500～1000.The processing condition of low-temp reaction section are: reaction pressure is 6～18MPa, better is 12～16MPa; Temperature of reaction is 300～420 ℃, is 350～400 ℃ preferably; Liquid hourly space velocity is 0.2～4.0h
-1, be preferably 0.8～2h
-1Hydrogen to oil volume ratio (under the standard pressure) is 500～2500, better is 800～1500.
Heavy residual oil raw material enters the low-temp reaction section and carries out effective hydrogenation saturated reaction, and then through Pintsch process, can improve liquid yield after the cracking of pyroreaction section, reduces the productive rate of coke simultaneously.
The present invention can adopt any existing hydrocracking catalyst for suspension bed, comprises oil soluble, water-soluble and other disperse type catalyzer.
The present invention recommends to adopt two pyroreaction sections and a low-temp reaction section.The low-temp reaction section is positioned between two pyroreaction sections.
Be that example is described in detail the present invention in conjunction with the accompanying drawings with this scheme below:
Wherein 1 is feed line, and 2 is catalyst line, and 3 is mixing tank, and 4,6,7,9,11,13,15,16,18 is pipeline, and 5 is pump, and 8 is high-temperature reactor, and 10 is the low-temp reaction device, and 12 is high-temperature reactor, and 14 is the high pressure low temperature separator, and 17 is caustic treater.
Its specific operation process is as follows:
Residual oil raw material and aqueous catalyst solution enter mixing tank 3 from pipeline 1 and 2 respectively.Mixing tank 3 can be a stirred pot, also can be a colloidal mill or static mixer or other conventional mixing equipment, and residual oil and aqueous catalyst solution are mixed.Charging after mixing mixes with the hydrogen that is fed by pipeline 6 in pipeline 7 through pipeline 4 and pump 5, enters high-temperature reactor 8.The logistics of coming out from the high-temperature reactor bottom enters low-temp reaction device 10 through pipeline 9.The logistics of coming out from low-temp reaction device 10 enters high-temperature reactor 12 through pipeline 11.Reaction product enters high pressure low temperature separator 14 via pipeline 13, isolates gas and liquid product.Liquid product is discharged by pipeline 16, and isolated gas enters caustic treater 17 through pipeline 15, discharges from pipeline 18 then.
Advantage of the present invention is:
1, adopts the processing method of the present invention can be when the processing poor-quality heavy residuum,, obtain liquid oil to greatest extent and produce coke and dry gas as far as possible less substantially not under the situation of green coke.
2, in the floating bed hydrogenation process, adopted homodisperse type catalyzer, effectively avoided the green coke of process, thereby made and do not contain solid particulate substantially in the tail oil.
For further specifying all main points of the present invention, enumerate following examples.
Embodiment 1-7
Test raw material is a vacuum residuum in the sand, and its character sees Table 1.
Subtract the slag feedstock property in table 1 sand
Project numerical value item number value
Density (20 ℃)/Kg/m
31024.8 V 143.6
Carbon residue/w% 20.73 Fe 8.16
Ultimate analysis/% Ni 43.4
C 83.52 four proximate analyses/w%
H 10.43 stable hydrocarbon 9.9
S 4.95 aromatic hydrocarbon 52.2
N 0.35 colloid 29.5
Metallic element/ug.g
-1Bituminous matter 8.4
By table 1 as seen, vacuum residuum density is big in the sand, and H/C is than low, the carboloy residue height, and sulphur content is up to 4.95w%, and gum level is 29.5w%, and asphalt content is 8.4w%, is the unmanageable poor residuum of the conventional method for modifying of a kind of usefulness.
The dreg-oil suspension bed three section hydrogenation reactions of this test explanation under the differential responses condition.Coke forming property characterizes to measure the toluene insolubles that generates in the oil.
The present invention adopts the water-soluble catalyst that contains molybdenum, cobalt, nickel and tungsten, and metal content 8.66w% in the catalyzer is a benchmark with stock oil, and the catalyzer add-on is calculated as 300ug.g by metal
-1
Three sections floating bed hydrogenation operational conditions of table 2 and reaction result
The reaction conditions of embodiment 1234567 pyroreaction section I
Temperature of reaction ℃ 430 440 450 438 442 434 438
Reaction pressure MPa 10 13 18 12 15 12 14
Air speed h
-11.0 1.5 1.7 2.0 1.6 1.1 1.1
The reaction conditions of hydrogen-oil ratio (V/V) 500 1,000 1,200 700 900 1,000 1000 low-temp reaction section II
Temperature of reaction ℃ 370 390 400 390 400 390 390
Reaction pressure MPa 10 13 18 12 15 12 14
Air speed h
-11.0 1.5 1.7 2.0 1.6 1.1 1.1
The reaction conditions of hydrogen-oil ratio (V/V) 500 1,000 1,000 700 900 1,000 1000 pyroreaction section III
Temperature of reaction ℃ 436 440 450 440 442 438 440
Reaction pressure MPa 10 13 18 12 15 12 14
Air speed h
-11.0 1.5 1.7 2.0 1.6 1.1 1.1
500 1,000 1,200 700 900 1,000 1000＞500 ℃ of bottoms conversion/w% 66.23 80.10 82.40 81.30 83.60 75.21 79.30 of hydrogen-oil ratio (V/V)
Toluene insolubles w% 0.23 0.54 0.76 0.78 0.65 0.56 0.62
Residual oil raw material and aqueous catalyst solution enter mixing tank 3 from pipeline 1 and 2 respectively, and residual oil and aqueous catalyst solution are mixed.Charging after mixing mixes with the hydrogen that is fed by pipeline 6 in pipeline 7 through pipeline 4 and pump 5, enters high-temperature reactor 8.The logistics of coming out from the high-temperature reactor bottom enters low-temp reaction device 10 through pipeline 9.The logistics of coming out from low-temp reaction device 10 enters high-temperature reactor 12 through pipeline 11.Reaction product enters high pressure low temperature separator 14 via pipeline 13, isolates gas and liquid product.Liquid product is discharged by pipeline 16, and isolated gas enters caustic treater 17 through pipeline 15, discharges from pipeline 18 then.
Embodiment 8～12
This test is the comparative examples that adopts single hop high temperature suspension bed hydrogenation process.
Residual oil raw material and aqueous catalyst solution enter mixing tank 3 from pipeline 1 and 2 respectively, and residual oil and aqueous catalyst solution are mixed.Charging after mixing mixes with the hydrogen that is fed by pipeline 6 in pipeline 7 through pipeline 4 and pump 5, enters high-temperature reactor 8.The logistics of coming out from the high-temperature reactor bottom directly enters high pressure low temperature separator 14, isolates gas and liquid product.Liquid product is discharged by pipeline 16, and isolated gas enters caustic treater 17 through pipeline 15, discharges from pipeline 18 then.
Table 3 single hop floating bed hydrogenation operational condition and reaction result
The reaction conditions of embodiment 89 10 11 12 pyroreaction sections
Temperature of reaction ℃ 430 440 438 442 434
Reaction pressure MPa 10 13 12 14 12
Air speed h
-11.0 1.0 1.0 1.0 1.1
500 700 700 900 1000＞500 ℃ of bottoms conversion/w% 58.08 72.31 72.00 75.03 69.21 of hydrogen-oil ratio (V/V)
Toluene insolubles w% 0.43 1.03 1.00 2.10 0.93
From the test-results of table 2 and table 3 as can be seen, take multistage suspension bed hydroprocessing technology can improve the yield of benzoline significantly, reduce the content that generates toluene insolubles in the oil simultaneously, help the long-term stability running of device.
Claims (5)
1. method of handling inferior heavy, residual oil, it is characterized in that at first hydrogenation catalyst being dispersed in the stock oil, the stock oil and the hydrogen that will contain catalyzer again are mixed into multistage suspension bed hydroprocessing reactor, hydrogenation and scission reaction take place in heavy residual oil in reactor, change into low boiler cut; Described multistage suspension bed hydroprocessing reactor comprises one or more pyroreaction sections and one or more low-temp reaction section, and the pyroreaction section is positioned at before the low-temp reaction section and the low-temp reaction section is interspersed; The processing condition of wherein said pyroreaction section are: reaction pressure is 6～18MPa, and temperature of reaction is 400～500 ℃, and liquid hourly space velocity is 0.2～4.0h
-1, hydrogen to oil volume ratio is 100～1200; The processing condition of described low-temp reaction section are: reaction pressure is 6～18MPa, and temperature of reaction is 300～420 ℃, and liquid hourly space velocity is 0.2～4.0h
-1, hydrogen to oil volume ratio is 500～2500.
2. in accordance with the method for claim 1, it is characterized in that the total add-on of hydrogenation catalyst counts 50～400ug.g with metal
-1
3. in accordance with the method for claim 1, it is characterized in that the processing condition of described pyroreaction section are: reaction pressure 12～16MPa, temperature of reaction is 430～450 ℃; Liquid hourly space velocity is 1～2h
-1Hydrogen to oil volume ratio is 500～1000.
4. in accordance with the method for claim 1, the processing condition that it is characterized in that described low-temp reaction section are: reaction pressure is 12～16MPa; Temperature of reaction is 350～400 ℃; Liquid hourly space velocity is 0.8～2h
-1Hydrogen to oil volume ratio is 800～1500.
5. in accordance with the method for claim 1, it is characterized in that said multistage suspension bed hydroprocessing reactor comprises two pyroreaction sections and a low-temp reaction section, the low-temp reaction section is positioned between two pyroreaction sections.
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| CN 00123222 CN1123631C (en) | 2000-11-08 | 2000-11-08 | Technological process of treating infertor heavy and residual oil |
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| CN 00123222 CN1123631C (en) | 2000-11-08 | 2000-11-08 | Technological process of treating infertor heavy and residual oil |
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| CN1123631C true CN1123631C (en) | 2003-10-08 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051207A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for enhancing mass transfer through suspension bed hydrogenation technology |
| CN104549276A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Thermal cracking catalyst for residual oil in presence of hydrogen, and preparation and application thereof |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102234534B (en) * | 2010-04-28 | 2014-01-15 | 中国石油化工股份有限公司 | Method for processing inferior heavy oil |
| CN104513675B (en) * | 2013-09-27 | 2017-01-11 | 中国石油化工股份有限公司 | Heavy oil hydrogenation transformation method |
| CN104549278B (en) * | 2013-10-28 | 2017-07-25 | 中国石油化工股份有限公司 | A kind of residual oil bifunctional catalyst and its preparation and application |
| CN104560176B (en) * | 2013-10-29 | 2017-03-01 | 中国石油化工股份有限公司 | A kind of heavy oil hydrogenation conversion method |
| CN104785171B (en) * | 2014-01-21 | 2017-09-12 | 北京金菲特能源科技有限公司 | A kind of universal heavy charge hydrogenation lighting device |
| CN104403686B (en) * | 2014-11-27 | 2016-09-07 | 波露明（北京）科技有限公司 | A kind of method for hydrogen cracking of heavy oil |
| CN108085057B (en) * | 2017-12-28 | 2020-05-01 | 北京三聚环保新材料股份有限公司 | Heavy oil hydrocracking process |
-
2000
- 2000-11-08 CN CN 00123222 patent/CN1123631C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051207A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for enhancing mass transfer through suspension bed hydrogenation technology |
| CN104549276A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Thermal cracking catalyst for residual oil in presence of hydrogen, and preparation and application thereof |
| CN104549276B (en) * | 2013-10-28 | 2017-04-26 | 中国石油化工股份有限公司 | Thermal cracking catalyst for residual oil in presence of hydrogen, and preparation and application thereof |
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| CN1352232A (en) | 2002-06-05 |
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