CN201144230Y - System for preparing high-quality petrol by recombination of catalytic hydrocarbon - Google Patents
System for preparing high-quality petrol by recombination of catalytic hydrocarbon Download PDFInfo
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- CN201144230Y CN201144230Y CNU2007203020958U CN200720302095U CN201144230Y CN 201144230 Y CN201144230 Y CN 201144230Y CN U2007203020958 U CNU2007203020958 U CN U2007203020958U CN 200720302095 U CN200720302095 U CN 200720302095U CN 201144230 Y CN201144230 Y CN 201144230Y
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Abstract
The utility model discloses a high-quality gasoline preparation system through recombination of catalytic hydrocarbon, which consists of a distillation unit and an extraction system, and is characterized in that the primary hydrogenation device is connected with the distillation unit; the upper part of the distillation unit is provided with a light gasoline pipeline; the lower part of the distillation unit is connected with a heavy gasoline hydrogenation device via a heavy gasoline pipeline; the heavy gasoline hydrogenation device is connected with the extraction system via a pipeline; the lower part of the extraction system is connected with the light gasoline pipeline at the upper part of the distillation unit via a pipeline. Compared with the prior art, the catalyst of the primary hydrogenation device and the heavy gasoline hydrogenation device has higher pertinence, the content of sulfur in the mixed gasoline is lower, and the content of olefin is lower.
Description
Technical field
The utility model relates to a kind of system of catalyzing hydrocarbon for recombinant production of high-quality gasoline.
Background technology
Catalytic cracking, catalytic pyrolysis and heavy oil catalytic pyrolysis technology are the core technologies of oil refining, and catalytic cracking is divided into wax catalysis cracking, heavy oil fluid catalytic cracking; Be referred to as catalytic hydrocarbon from the generation oil of these explained hereafter, the gained catalytic hydrocarbon is through processing treatment, generally be the separation column fractionation, can fractionate out products such as net gas, liquefaction vapour, gasoline, diesel oil, heavy oil, wherein gasoline, more than 70% of diesel oil total supply on gasoline, the diesel oil occuping market.
More and more strictness along with environmental requirement, the standard of gasoline, diesel oil improves constantly, existing catalytic hydrocarbon is showed following deficiency through the fractionated processing and treating method of separation column: one is that the gasoline produced of this treatment process and the quality of diesel oil have much room for improvement: the olefin(e) centent of gasoline is higher, (RON) is on the low side for octane value, diesel-fuel cetane number is on the low side, and stability is undesirable; The 2nd, above-mentioned treatment process can not be produced the gasoline of multiple label simultaneously, and range of product is single; The 3rd, the demand in the diesel oil of being produced, the ratio of gasoline and market does not match, and diesel oil can not satisfy the demands, and gasoline supply exceed demand.
In order to address the above problem, the patent No. is that the Chinese invention patent of 03148181.7 " catalytic hydrocarbon reorganization treatment process " provides a kind of catalytic hydrocarbon reorganization treatment process, and the patent No. is respectively 200310103541.9 and 200310103540.4 and discloses its improvement patent, relate to water wash system and solvent recuperation, but all do not relate to the problem of how to fall sulphur and falling alkene in these disclosed patents.
Present GB17930 gasoline standard requires sulphur content to be not more than 0.05% (wt), olefin(e) centent to be not more than 35% (v), benzene content is not more than 2.5% (v), most refinerys can guarantee quality of gasoline.But the national III gasoline standard that is about to implement in 2010 requires: sulphur content is not more than 0.015% (wt), olefin(e) centent and is not more than 30% (v), benzene content is not more than 1% (v).For most refinery, must require in the face of higher national IV gasoline standard: sulphur content is not more than 0.005% (wt), alkene and is not more than 25% (v) or lower.The quality of gasoline solution must be considered the transition from national III gasoline standard to national IV gasoline standard, and programme should be disposable according to national IV gasoline standard programme preferably.
Because ratio and developed country's difference of each blend component is very big in China's gasoline products, catalytically cracked gasoline occupies very high ratio, and reformed gasoline, gasoline alkylate proportion are less, and this situation is with long-term existence.Therefore, the quality of gasoline upgrading problem of falling sulphur and falling alkene to be solved relates generally to the problem of catalytic gasoline.
It is generally acknowledged, the 5-10% of total sulfur will enter gasoline in the catalytically cracked material,, secondary processing catalytic cracking ability very little according to China's refinery fcc raw material hydrofining ability is big and the characteristics of residuum coking are arranged, the about 200ppm of refinery catalytic gasoline sulphur content of processing low-sulfur (sulfur-bearing 0.3%) crude oil, the crude oil of processing sulfur-bearing 0.8%, the about 900ppm of sulphur content in the catalytic gasoline, therefore, the difficult point of quality of gasoline upgrading changes the problem of sulphur into from alkene.The improvement of catalytic cracking process or catalyzer can not fundamentally solve the problem of sulphur, the catalytically cracked material hydrogenating desulfurization is because investment is big, working cost is high, existing refinery condition is limited and impossible large-scale application, and it is also inapplicable for the refinery of the low sulphur-bearing crude of processing, simultaneously, catalytic cracking unit excessively reduces the loss that alkene also can aggravate light-end products and gasoline octane rating (RON).
Therefore, provide the treatment system of the high blended gasoline of a kind of low-cost preparation low sulfur content, low olefin-content and octane value (RON) just to become the technical barrier that this technical field is badly in need of solution.
Summary of the invention
The purpose of this utility model provides a kind of catalytic hydrocarbon recombination system of gasoline of low-cost preparation low sulfur content, low olefin-content and boosting of octane rating (RON).
For achieving the above object, the utility model is taked following technical scheme:
A kind of system of catalyzing hydrocarbon for recombinant production of high-quality gasoline comprises water distilling apparatus and extraction system, it is characterized in that: the front-end hydrogenation device is connected with water distilling apparatus, and described water distilling apparatus top is provided with the petroleum naphtha pipeline; Described water distilling apparatus bottom is connected with the heavy petrol hydrogenation unit by the heavy petrol pipeline; Described heavy petrol hydrogenation unit is connected with described extraction system by pipeline; The bottom of described extraction system is connected by the petroleum naphtha pipeline of pipeline with described water distilling apparatus top.
A kind of method of catalyzing hydrocarbon for recombinant production of high-quality gasoline, its step is as follows: stable gasoline earlier by the hydrogenation unit hydrogenation, is entered water distilling apparatus then and carries out fractionation, fractionate out petroleum naphtha and heavy petrol; Described petroleum naphtha steams by water distilling apparatus top; The hydrotreatment in hydrogenation unit of described heavy petrol enters then and carries out extracting and separating in the extraction system, isolates aromatic hydrocarbons and raffinates oil; The petroleum naphtha that described aromatic hydrocarbons steams by pipeline and water distilling apparatus top is in harmonious proportion and uses, and the described direct extraction of raffinating oil is as feed ethylene.
A kind of preferred version is characterized in that: described heavy petrol enters after the part hydrotreatment in hydrogenation unit and carries out extracting and separating in the extraction system.
A kind of preferred version is characterized in that: the tower top temperature of described water distilling apparatus is 82～86 ℃, and column bottom temperature is 190～192 ℃; The tower top pressure of described water distilling apparatus is 0.11～0.28MPa (cutting off), and tower bottom pressure is 0.12～0.30MPa (cutting off); The boiling range of described petroleum naphtha is controlled at 30 ℃～80 ℃; The boiling range of described heavy petrol is controlled at 80 ℃～205 ℃.
A kind of preferred version is characterized in that: the tower top temperature of described water distilling apparatus is 82～86 ℃, and column bottom temperature is 190～192 ℃; The tower top pressure of described water distilling apparatus is 0.2MPa (cutting off), and tower bottom pressure is 0.25MPa (cutting off); The boiling range of described petroleum naphtha is controlled at 30 ℃～90 ℃; The boiling range of described heavy petrol is controlled at 90 ℃～205 ℃.
A kind of preferred version is characterized in that: the tower top temperature of described water distilling apparatus is 82～86 ℃, and column bottom temperature is 190～192 ℃; The tower top pressure of described water distilling apparatus is 0.2MPa (cutting off), and tower bottom pressure is 0.25MPa (cutting off); The boiling range of described petroleum naphtha is controlled at 30 ℃～90 ℃; The boiling range of described heavy petrol is controlled at 90 ℃～205 ℃.
A kind of preferred version is characterized in that: the catalyzer in the described gasoline hydrogenation device is selective hydrogenation catalyst GHT-20; The volume space velocity ratio of described gasoline hydrogenation device is 2～3; Hydrogen/oil volume ratio is 150～200; Service temperature is 230～240 ℃, and working pressure is 0.6～1.0MPa (cutting off).
A kind of preferred version is characterized in that: the physico-chemical property of the selective hydrogenation catalyst GHT-20 in the described gasoline hydrogenation device is as shown in table 1 below.
Table 1
| Index name | Unit | Index |
| Outward appearance | The grey trilobal cross | |
| Specification | mm | Φ1.5-2.0 |
| Intensity | N/cm | 170 |
| Bulk density | g/ml | 0.70 |
| Specific surface | m 2/g | 180 |
| Pore volume | ml/g | 0.5-0.6 |
| WO 3 | m％ | 6.6 |
| NiO | m％ | 2.1 |
| C 0O | m％ | 0.16 |
A kind of preferred version is characterized in that: the catalyzer in the described heavy petrol hydrogenation unit is whole hydrogenation catalyst GHT-22; The volume space velocity ratio of described heavy petrol hydrogenation unit is 2～3; Hydrogen/oil volume ratio is 250～300; Service temperature is 275～310 ℃, and working pressure is 1.2～2.3MPa (cutting off).
A kind of preferred version is characterized in that: the physico-chemical property of the whole hydrogenation catalyst GHT-22 in the described heavy petrol hydrogenation unit is as shown in table 2 below.
Table 2
The used water distilling apparatus of the utility model is that the patent No. is a disclosed Distallation systm in the Chinese invention patent of 03148181.7 " catalytic hydrocarbon reorganization treatment process ".It is disclosed extraction system in 200310103541.9 and 200310103540.4 that described extraction system uses the patent No., comprises solvent recuperation and water wash system.
The used hydrogenation unit of the utility model is existing hydrogenation unit, comprises process furnace, interchanger, high-pressure separator, atmospheric condenser, water condenser etc.
Beneficial effect:
Compared with prior art, the advantage of the system of catalyzing hydrocarbon for recombinant production of high-quality gasoline of the present utility model is: the catalyst aims catalytic hydrocarbon of used gasoline hydrogenation device, the catalyst aims heavy petrol of described heavy petrol hydrogenation unit, the parameter of described hydrogenation unit has more specific aim, the sulphur content of gained blended gasoline is lower, olefin(e) centent also lower (below 1%) meets the requirement of GB four.
Below by the drawings and specific embodiments the utility model is described further, but and does not mean that restriction the utility model protection domain.
Description of drawings
Fig. 1-1 is the schematic flow sheet of the utility model embodiment 1.
Fig. 1-2 is the schematic flow sheet of the utility model embodiment 2 and 3.
Embodiment
Embodiment 1
As Figure 1-1, be the schematic flow sheet of one of the utility model embodiment.With boiling range is 30-205 ℃, and sulphur content is 100ppm, and mercaptans content is 5ppm, and olefin(e) centent is 30%, and (v), diene content is 0.1% (v), aromaticity content is that 15% (v), octane value (RON) is 89, and density is 728 kilograms/meter
3Stable gasoline (catalytic gasoline) in hydrogenation unit 3-1, carry out hydrotreatment earlier with 100,000 tons/year flow, the catalyzer among the described hydrogenation unit 3-1 is selective hydrogenation catalyst GHT-20; The volume space velocity ratio of described hydrogenation unit 3-1 is 2; Hydrogen/oil volume ratio is 150; Service temperature is 230 ℃, and working pressure is 0.6MPa (cutting off); In distillation tower 1, cut fractionation then, the tower top temperature of distillation tower 1 is 82 ℃, column bottom temperature is 190 ℃, tower top pressure is 0.2MPa (cutting off), tower bottom pressure is 0.25MPa (cutting off), fractionation obtains petroleum naphtha and heavy petrol respectively, and described petroleum naphtha (boiling range is 30-80 ℃) steams by distillation tower 1 top, and its total amount of steaming is 40,000 tons/year; Described heavy petrol (boiling range is 80-205 ℃) enters hydrogenation unit 3-2 hydrotreatment with 60,000 tons/year flows; Catalyzer among the described hydrogenation unit 3-2 is whole hydrogenation catalyst GHT-22; The volume space velocity ratio of described hydrogenation unit 3-2 is 2; Hydrogen/oil volume ratio is 250; Service temperature is 290 ℃, and working pressure is 1.2MPa (cutting off); Enter extracting and separating in the heavy petrol extraction system 2 by pipeline then, isolate aromatic hydrocarbons and raffinate oil; Solvent for use is the N-formyl morpholine in the described extraction system 2, and extraction temperature is 115 ℃, and solvent ratio (solvent/charging) is 3.5 (quality), and the washing of raffinating oil is than being 0.2 (quality), and the solvent recuperation temperature is 151 ℃, and solvent recuperation pressure is 2.0MPa (cutting off); Described aromatic hydrocarbons is in harmonious proportion with 1.5 ten thousand tons/year flow and described petroleum naphtha, described raffinating oil with 4.5 ten thousand tons/year flow as the high-quality ethylene extraction.
The boiling range of gained blended gasoline is 30-205 ℃, and sulphur content is 9.64ppm, and mercaptans content is less than 1ppm, olefin(e) centent is 17.7%, and (v), diene content is that (v), aromaticity content is 25.5% (v) less than 0.01%, octane value (RON) is 93.7, and density is 705.5 kilograms/meter
3, produced quantity is 5.5 ten thousand tons/year.
The boiling range of gained high-quality ethylene is 80-205 ℃, and sulphur content is 2.0ppm, and mercaptans content is less than 1ppm, olefin(e) centent is that (v), diene content is that (v), aromaticity content is 3.0% (v) less than 0.01% less than 0.1%, octane value (RON) is 81.0, and density is 760.0 kilograms/meter
3, produced quantity is 4.5 ten thousand tons/year.
The physico-chemical property of described selective hydrogenation catalyst GHT-20 is as shown in table 3 below.
Table 3
| Index name | Unit | Index |
| Outward appearance | The grey trilobal cross | |
| Specification | mm | Φ1.7 |
| Intensity | N/cm | 170 |
| Bulk density | g/ml | 0.70 |
| Specific surface | m 2/g | 180 |
| Pore volume | ml/g | 0.55 |
| WO 3 | m％ | 6.6 |
| NiO | m％ | 2.1 |
| C 0O | m％ | 0.16 |
The physico-chemical property of described whole hydrogenation catalyst GHT-22 is as shown in table 4 below.
Table 4
The used measuring method of the utility model is (down together):
1, boiling range: GB/T6536-1997 measured for petroleum product distillation method;
2, sulphur content: the total sulfur content assay method (ultraviolet fluorescence method) of SH/T0689-2000 light hydrocarbon and motor spirit and other oil products;
3, mercaptan sulfur: mercaptan sulfur assay method (potentiometric titration) in the GB/T1792-1988 distillate fuel oil;
4, alkene: GB/T11132-2002 liquid petroleum product hydro carbons assay method (fluorescent indicator adsorption method);
5, aromatic hydrocarbons: GB/T11132-2002 liquid petroleum product hydro carbons assay method (fluorescent indicator adsorption method);
6, octane value: GB/T5487 testing octane number of gasoline method (organon);
7, density: GB/T1884-2000 crude oil and liquid petroleum product density experiment chamber assay method (densimeter method);
8, the mensuration of diene: volumetry.
9, hydrogenation catalyst analytical procedure:
| Chemical constitution | Analytical procedure | The petrochemical industry standard that adopts |
| NiO | Colorimetry | SH/T0346-1992 |
| CoO | Colorimetry | SH/T0345-1992 |
| WO 3 | Colorimetry | |
| Physical property | Analytical procedure | The instrument that uses |
| Surface-area | Low-temperature nitrogen adsorption method | 2400 types absorption instrument |
| Pore volume | Mercury penetration method | Auto Pore II 9200 |
| Intensity | The crush strength assay method | DL II type intelligence granule strength determinator |
| Bulk density | Weighing method |
Shown in Fig. 1-2, be two the schematic flow sheet of the utility model embodiment.With boiling range is 30-205 ℃, and sulphur content is 2000ppm, and mercaptans content is 50ppm, and olefin(e) centent is 40%, and (v), diene content is 1.0% (v), aromaticity content is that 19% (v), octane value (RON) is 91, and density is 728 kilograms/meter
3Stable gasoline (catalytic gasoline) in hydrogenation unit 3-1, carry out hydrotreatment earlier with 100,000 tons/year flow, the catalyzer among the described hydrogenation unit 3-1 is selective hydrogenation catalyst GHT-20; The volume space velocity ratio of described hydrogenation unit 3-1 is 3; Hydrogen/oil volume ratio is 200; Service temperature is 240 ℃, and working pressure is 1.0MPa (cutting off); In distillation tower 1, cut fractionation then, the tower top temperature of distillation tower 1 is 86 ℃, column bottom temperature is 192 ℃, tower top pressure is 0.2MPa (cutting off), tower bottom pressure is 0.25MPa (cutting off), fractionation obtains petroleum naphtha and heavy petrol respectively, and described petroleum naphtha (boiling range is 30-90 ℃) steams by distillation tower 1 top, and its total amount of steaming is 4.3 ten thousand tons/year; Described heavy petrol (boiling range is 90-205 ℃) enters hydrogenation unit 3-2 hydrotreatment with 5.7 ten thousand tons/year flows; Catalyzer among the described hydrogenation unit 3-2 is whole hydrogenation catalyst GHT-22; The volume space velocity ratio of described hydrogenation unit 3-2 is 3; Hydrogen/oil volume ratio is 300; Service temperature is 310 ℃, and working pressure is 2.0MPa (cutting off); Enter extracting and separating in the heavy petrol extraction system 2 by pipeline then, isolate aromatic hydrocarbons and raffinate oil; Solvent for use is the N-formyl morpholine in the described extraction system 2, and extraction temperature is 115 ℃, and solvent ratio (solvent/charging) is 3.5 (quality), and the washing of raffinating oil is than being 0.2 (quality), and the solvent recuperation temperature is 151 ℃, and solvent recuperation pressure is 0.112MPa (cutting off); Described aromatic hydrocarbons is in harmonious proportion with 2.1 ten thousand tons/year flow and described petroleum naphtha, described raffinating oil with 3.6 ten thousand tons/year flow as the high-quality ethylene extraction.
The boiling range of gained blended gasoline is 30-205 ℃, and sulphur content is 43.64ppm, and mercaptans content is less than 1ppm, olefin(e) centent is 21.9%, and (v), diene content is that (v), aromaticity content is 28.2% (v) less than 0.01%, octane value (RON) is 96.0, and density is 723.0 kilograms/meter
3, produced quantity is 6.4 ten thousand tons/year.
The boiling range of gained high-quality ethylene is 90-205 ℃, and sulphur content is 2.0ppm, and mercaptans content is less than 1ppm, olefin(e) centent is that (v), diene content is that (v), aromaticity content is 3.0% (v) less than 0.01% less than 0.1%, octane value (RON) is 79.4, and density is 760.0 kilograms/meter
3, produced quantity is 3.6 ten thousand tons/year.
Embodiment 3
Shown in Fig. 1-2, be three the schematic flow sheet of the utility model embodiment.With boiling range is 30-205 ℃, and sulphur content is 2000ppm, and mercaptans content is 50ppm, and olefin(e) centent is 40%, and (v), diene content is 1.0% (v), aromaticity content is that 19% (v), octane value (RON) is 91, and density is 728 kilograms/meter
3Stable gasoline (catalytic gasoline) in hydrogenation unit 3-1, carry out hydrotreatment earlier with 100,000 tons/year flow, the catalyzer among the described hydrogenation unit 3-1 is selective hydrogenation catalyst GHT-20; The volume space velocity ratio of described hydrogenation unit 3-1 is 3; Hydrogen/oil volume ratio is 200; Service temperature is 240 ℃, and working pressure is 1.0MPa (cutting off); In distillation tower 1, cut fractionation then, the tower top temperature of distillation tower 1 is 86 ℃, column bottom temperature is 192 ℃, tower top pressure is 0.2MPa (cutting off), tower bottom pressure is 0.25MPa (cutting off), fractionation obtains petroleum naphtha and heavy petrol respectively, and described petroleum naphtha (boiling range is 30-90 ℃) steams by distillation tower 1 top, and its total amount of steaming is 4.3 ten thousand tons/year; Described heavy petrol (boiling range is 90-205 ℃) enters hydrogenation unit 3-2 with 5.7 ten thousand tons/year flows and carries out the selective hydrogenation processing; Catalyzer among the described hydrogenation unit 3-2 is selective hydrogenation catalyst GHT-20; The volume space velocity ratio of described hydrogenation unit 3-2 is 3; Hydrogen/oil volume ratio is 290; Service temperature is 275 ℃, and working pressure is 2.3MPa (cutting off); Enter extracting and separating in the heavy petrol extraction system 2 by pipeline then, isolate aromatic hydrocarbons and raffinate oil; Solvent for use is the N-formyl morpholine in the described extraction system 2, and extraction temperature is 115 ℃, and solvent ratio (solvent/charging) is 3.5 (quality), and the washing of raffinating oil is than being 0.2 (quality), and the solvent recuperation temperature is 151 ℃, and solvent recuperation pressure is 0.112MPa (cutting off); Described aromatic hydrocarbons is in harmonious proportion with 2.1 ten thousand tons/year flow and described petroleum naphtha, described raffinating oil with 3.6 ten thousand tons/year flow as the high-quality ethylene extraction.
The boiling range of gained blended gasoline is 30-205 ℃, and sulphur content is 43.31ppm, and mercaptans content is less than 1ppm, olefin(e) centent is 22.6%, and (v), diene content is that (v), aromaticity content is 28.21% (v) less than 0.01%, octane value (RON) is 95.7, and density is 723.0 kilograms/meter
3, produced quantity is 6.4 ten thousand tons/year.
The boiling range of gained high-quality ethylene is 90-205 ℃, and sulphur content is 2.0ppm, and mercaptans content is less than 1ppm, olefin(e) centent is 7.0%, and (v), diene content is that (v), aromaticity content is 3.0% (v) less than 0.01%, octane value (RON) is 79.4, and density is 740.0 kilograms/meter
3, produced quantity is 3.6 ten thousand tons/year.
Claims (1)
1, a kind of system of catalyzing hydrocarbon for recombinant production of high-quality gasoline comprises water distilling apparatus and extraction system, it is characterized in that: the front-end hydrogenation device is connected with water distilling apparatus, and described water distilling apparatus top is provided with the petroleum naphtha pipeline; Described water distilling apparatus bottom is connected with the heavy petrol hydrogenation unit by the heavy petrol pipeline; Described heavy petrol hydrogenation unit is connected with extraction system by pipeline; The bottom of described extraction system is connected by the petroleum naphtha pipeline of pipeline with described water distilling apparatus top.
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| CNU2007203020958U CN201144230Y (en) | 2007-11-09 | 2007-11-09 | System for preparing high-quality petrol by recombination of catalytic hydrocarbon |
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| CNU2007203020958U CN201144230Y (en) | 2007-11-09 | 2007-11-09 | System for preparing high-quality petrol by recombination of catalytic hydrocarbon |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429448B (en) * | 2007-11-09 | 2012-11-14 | 丁冉峰 | System and method for catalyzing hydrocarbon for recombinant production of high-quality gasoline |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101429448B (en) * | 2007-11-09 | 2012-11-14 | 丁冉峰 | System and method for catalyzing hydrocarbon for recombinant production of high-quality gasoline |
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Denomination of utility model: System and method for catalyzing hydrocarbon for recombinant production of high-quality gasoline Effective date of registration: 20140924 Granted publication date: 20081105 Pledgee: Zhongguancun Beijing technology financing Company limited by guarantee Pledgor: Beijing Golden Dragon Engineering Technology Co., Ltd.|Ding Ranfeng Registration number: 2014990000793 |
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Date of cancellation: 20160517 Granted publication date: 20081105 Pledgee: Zhongguancun Beijing technology financing Company limited by guarantee Pledgor: Beijing Golden Dragon Engineering Technology Co., Ltd.|Ding Ranfeng Registration number: 2014990000793 |
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Granted publication date: 20081105 |