CN100451091C - Method for reducing the content of olefin in high olefin gasoline - Google Patents
Method for reducing the content of olefin in high olefin gasoline Download PDFInfo
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- CN100451091C CN100451091C CNB200410022857XA CN200410022857A CN100451091C CN 100451091 C CN100451091 C CN 100451091C CN B200410022857X A CNB200410022857X A CN B200410022857XA CN 200410022857 A CN200410022857 A CN 200410022857A CN 100451091 C CN100451091 C CN 100451091C
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- 239000003502 gasoline Substances 0.000 title claims abstract description 92
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 63
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000005516 engineering process Methods 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 8
- 238000010517 secondary reaction Methods 0.000 claims description 6
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000004523 catalytic cracking Methods 0.000 description 14
- 239000003208 petroleum Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000003921 oil Substances 0.000 description 8
- 241000282326 Felis catus Species 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001833 catalytic reforming Methods 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000019628 coolness Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000003562 lightweight material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Abstract
The present invention provides a method for reducing the content of olefin in high olefin gasoline. The gasoline with a high olefinic content enters a rectifying tower and is cut in the rectifying tower, a light gasoline fraction with a high olefinic content is separated from the upper part of the tower, and a fraction with a low olefinic content is a tower pot. The light gasoline fraction on the upper part of the tower is directly injected at the middle part of a riser reactor by an MGD technical skill and an MIP technical skill, or is modified by using any one of FDFCC technical skills. The heavy gasoline fraction withdrawn from the tower pot is mixed with secondary reacted gasoline, and then enters a following working section with the secondary reacted gasoline. The method can obviously reduce the olefinic content in residual gasoline, and greatly reduce the energy consumption of a whole device.
Description
Affiliated technical field
The invention belongs to rectifying, the catalysis conversion method of petroleum hydrocarbon, specifically, is to belong to rectifying, the catalysis conversion method that reduces olefin(e) centent in the gasoline.
Background technology
Along with countries in the world for to environmental protection requirement, especially the olefin(e) centent of motor spirit has been made very strict regulation, though the reformulated gasoline standard that the every country in the world formulates is not quite similar, a total principle is that olefin(e) centent weighs below the % 20 in the gasoline component.As everyone knows, the olefin(e) centent of catalytic cracking catalytic gasoline is 35wt%～65wt%, because in the composition of Chinese commodity gasoline is to come from catalytic cracking unit more than 70%, lack devices such as corresponding catalytic reforming, alkylation, isomerization and etherificate simultaneously, thereby, the blend component of Chinese commodity gasoline is less, and rationally not near.
Alkene in the gasoline is because its poor stability easily forms colloid; Simultaneously the too high gasoline of olefin(e) centent can cause also that alkene can be oxidized to settling under the temperature condition of fuel of internal combustion engine system in vehicle traveling process, and it is insufficient to cause burning, and makes hydrocarbon polymer, CO (carbon monoxide converter) emission increase contaminate environment.
Gasoline for high olefin content generally can satisfy the standard of reformulated gasoline by calling in the gasoline component of low olefin-content.But this method must need to obtain low alkene stop bracket gasoline cut by newly-built a series of devices, invests big and unreasonable economically.
The MGD technology that Research Institute of Petro-Chemical Engineering invents is disclosed among the CN1279270A---a kind of high-yield diesel oil and liquefied gas can reduce the catalytic cracking process of content of olefin in gasoline simultaneously, this method is injected into the catalysis raw gasline in a riser tube with four reaction areas or the fluidized-bed reactor and with reaction secondary reaction takes place, thereby make the olefin(e) centent of gasoline be reduced, but this method need be injected a large amount of raw gasline, account for 25 heavy % of combined feed total feed, could reduce olefin(e) centent 5～10 body % in the gasoline.
CN1245202A discloses the MIP technology that Research Institute of Petro-Chemical Engineering invents---and the catalytic cracking process of isoparaffin is produced in maximization, this technology is that the bottom that conventional cracking stock enters riser tube contacts with catalyzer, catalyzer after the oil gas that the reaction back generates goes upward to the riser tube middle part and lowers the temperature contacts and continues reaction, and reaction back effluent enters settling vessel; Reaction product isolated, reclaimable catalyst is divided into two portions after stripping, regeneration, and wherein a part enters the riser tube bottom, and another part enters the middle part of riser tube after cooling.This method can make in the gasoline olefin(e) centent be reduced to 12.32 heavy %.
Disclosing a kind of catalysis conversion method of gasoline upgrading among the CN1244568A, is that the low octane value gasoline after the preheating is entered from riser tube bottom, and the gasoline that is rich in alkene enters from the middle part of riser tube, contact with catalyzer, and reaction afterwards effluent enters settling vessel; Reaction product isolated, reclaimable catalyst are returned riser tube and are used after stripping, regeneration.This method can make the olefin(e) centent of gasoline be reduced to below the 20 heavy %.
Disclose among the CN1401741A refining of Luoyang Petrochemical engineering corporation FDFCC technology---the adaptable multieffect double lifting leg technology developed, the inferior patrol that this method is primarily aimed at high olefin content carries out upgrading, it is characterized in that comprising a conventional heavy oil catalytic cracking process and an inferior patrol catalyzed conversion upgrading process.Heavy oil carries out conventional catalytic cracking reaction at the heavy oil riser reactor, inferior patrol carries out the catalyzed conversion upgrading at the gasoline rising pipe reactor, two shared catalyst regenerators of process, use is with a kind of catalytic cracking catalyst, the result can make the olefin(e) centent of inferior patrol reduce by 15～50 volume percentage points, and gasoline octane rating (RON) improves 0.2～2 unit; Content of sulfur in gasoline reduces by 10～30%.
Above-mentioned patented method just reduces olefin content in gasoline from the improvement of catalytic cracking process, and need carry out bigger change to existing catalytic unit and just can implement.
Summary of the invention
The objective of the invention is on existing technical foundation, provide a kind of method that the elder generation of olefin(e) centent separates catalytic reforming again in the gasoline that reduces, to satisfy the standard of reformulated gasoline.
To be methods of having adopted rectifying carry out fine cut to the gasoline of high olefin content to characteristics of the present invention, high olefin content component in the high olefin gasoline is cut out, and then with the high olefin component separated can be by MGD Technology, MIP Technology, directly be recycled into riser reactor middle part or adopt any technology in the FDFCC Technology to carry out upgrading.
Method provided by the invention is: the gasoline of high olefin content is entered in the rectifying tower, cut in rectifying tower, the higher relatively light gasoline fraction of olefin(e) centent is isolated on tower top, and the tower still is the lower cut of olefin(e) centent.Tower top light gasoline fraction is again by MGD Technology, MIP Technology, directly be recycled into riser reactor middle part or adopt any technology in the FDFCC Technology to carry out upgrading; The heavy naphtha that the tower still is extracted out goes to follow-up workshop section to handle after being in harmonious proportion with the gasoline of crossing through secondary reaction more in the lump.
Method provided by the invention can be implemented by following proposal:
Gasoline through the high olefin content after the preheating enters rectifying tower from the middle part, and set reboiler can adopt steam or other thermal barrier as thermal source at the bottom of the tower, and cat head is established condenser, and cat head is established cold reflux.The gasoline of high olefin content carries out rectifying in tower, light constituent steams after cooling from cat head as gas, a part turns back to rectifier as backflow, a part enters the riser tube bottom as the reformulated gasoline component, mix with the relative heavier gasoline fraction that the tower still is extracted out again through the gasoline fraction behind the upgrading, enter the gasoline desulfur operation.
The operational condition of rectifying tower: tower top temperature is: 50 ℃～110 ℃, be preferably 60 ℃～90 ℃; Tower still temperature is: 120 ℃～160 ℃, be preferably: 130 ℃～150 ℃.
The boiling range scope of cat head petroleum naphtha is: 30 ℃～120 ℃, be preferably 30 ℃～110 ℃, and be preferably 35 ℃～95 ℃.
The gasoline of the high olefin content that the present invention is used specifically is selected from a kind of in catalytically cracked gasoline, coker gasoline, the pyrolysis gasoline or their mixture.
The rectifying tower that the present invention is used both can be valve tray, also can be sieve-tray tower and packing tower.Its tower diameter can be the equal diameter rectifying tower, also can be the reducing rectifying tower that the top tower diameter is little, the bottom tower diameter is big.
The invention has the advantages that:
1, carries out fine cut by gasoline, its petroleum naphtha that is rich in olefin component is cut out, can obviously reduce the residue olefin content in gasoline high olefin content.
2, the petroleum naphtha that will be rich in olefin component carries out secondary reaction by being recycled into the reaction riser tube, thereby can make the gasoline freshening accomplish freshening selectively, and the alkene that more helps in the gasoline reacts, and has improved the effect of gasoline catalyzing and olefine reducing.
3, this method can be in MGD Technology, MIP Technology, directly be recycled into riser reactor middle part or adopt on the technology bases such as FDFCC technology, can further reduce gasoline freshening ratio, reduced the energy consumption of whole device widely.
Description of drawings
Below in conjunction with accompanying drawing method provided by the present invention is given further instruction.
Fig. 1 is a schematic flow sheet of the present invention, and the shape and size of equipment and pipeline are not limited by accompanying drawing, but determines as the case may be.
1,3,7,8,10,13,14 all represent pipeline among Fig. 1; 2 is rectifying tower, and 4 is condenser, and 5 is condensate drum, and 6,11 is pump, and 9 is catalytic cracking unit, and 11 are rectifying Tata still reboiler.
As shown in Figure 1, the flow process of above-mentioned embodiment is as follows:
High olefin gasoline enters the middle part of rectifying tower 2 through pipeline 1, after rectifying tower 2 process rectifying separation, the light constituent that is rich in alkene is after pipeline 3, condenser 4 coolings, enter overhead condensation flow container 5, after the liquid of condensate drum is extracted out by pump 6, be divided into two-way, wherein one the tunnel return rectifying tower as cold reflux through pipeline 7, another road removes to take place secondary reaction through pipeline 8 to catalytic cracking unit 9; Rectifying tower 2 tower stills are heated by bottom reboiler 11, tower bottoms by pump 12 extract out through pipeline 13 with mix follow up device by one of catalysis stable gasoline and carry out desulfuration purification through pipeline 10.
Embodiment
The following examples will be further specified the present invention, but be not therefore and restriction the present invention.
Embodiment: enter the rectifying tower middle part through the high olefin content gasoline after the heat exchange, after cat head cooling and the heating of tower still, high olefin gasoline is separated into petroleum naphtha and the lower heavy petrol two portions of olefin(e) centent that are rich in alkene; Petroleum naphtha is again by MGD Technology, MIP Technology, directly be recycled into riser reactor middle part or adopt any technology in the FDFCC Technology to carry out secondary reaction to eliminate most of alkene wherein; Mix one with the heavy petrol of rectifying Tata still again through the gasoline of gained behind the upgrading and remove to carry out desulfuration purification.
Method provided by the invention is adopted in the present embodiment explanation, reduces the situation of olefin(e) centent in the gasoline on full scale plant.
Operational condition sees Table 1; Product distributes and sees Table 2; The character of gasoline products is listed in table 3.As can be seen from Table 3, alkene only accounted for 31.4 volume % during gasoline was formed, and the yield of propylene can reach 11.21 heavy %.
Comparative Examples 1
Compare with embodiment 1, different is, high olefin content gasoline is not cut, and carries out freshening but part high olefin content gasoline direct tapped into into catalytic cracking unit, and the reaction conditions of gasoline freshening ratio and catalytic cracking is substantially the same manner as Example 1.Resulting product distributes and sees Table 2; The character of gasoline products is listed in table 3.
The present embodiment explanation is done not simultaneously the cutting of cat head petroleum naphtha by adjusting the operational condition of rectifying tower, adopts method provided by the invention to reduce the situation of olefin(e) centent in the gasoline on full scale plant.
The reaction conditions of catalytic cracking upgrading is identical with embodiment 1, can see Table 1.
The character of petroleum naphtha boiling range cut coverage, gasoline products and product distribute and list in table 4.As can be seen from Table 4, the alkene during gasoline is formed only accounts between 28.6～34.2 volume %.
Embodiment 3
The present embodiment explanation is controlled the amount of extracting of cat head petroleum naphtha by adjusting the inlet amount of rectifying tower, thereby changes the situation of the freshening ratio of petroleum naphtha to the reduction content of olefin in gasoline.
The reaction conditions of catalytic cracking upgrading is except recycle ratio and embodiment 1 are inequality, and other condition is all identical with embodiment 1, can see Table 1.
The freshening amount of petroleum naphtha, the character of gasoline products and product distribute and list in table 5.As can be seen from Table 5, the alkene during gasoline is formed is between 33.2～40.5 volume %.
Table 1
| | Unit | Embodiment | 1 | Comparative Examples 1 |
| Terminator amount of gasoline stock oil atomizing steam amount promotes quantity of steam in advance and promotes dry gas amount stripped vapor amount stripped vapor quantitative response temperature regeneration temperature high olefin gasoline freshening amount petroleum naphtha freshening content of starting materials oil flow lightweight material oil flow reprocessed oil slurry flow recycle stock flow in advance | kg/h kg/h kg/h kg/h kg/h kg/h ℃ ℃ t/h t/h t/h t/h t/h t/h | 0 6600 800 2200 3065 1520 515 693 0 24 140 0 7.5 5.0 | 0 6600 800 2200 3065 1520 515 693 24 0 140 0 7.5 5.0 |
Table 2
| Product distributes, heavy % | |
Comparative Examples 1 |
| The loss of dry gas liquefied gas gasoline solar oil slurry oil coke adds up to | 3.87 25.75 37.68 21.47 1.13 9.56 0.54 100.0 | 4.39 23.60 38.65 20.03 1.48 9.40 0.45 100.0 |
| Transformation efficiency % gasoline+diesel oil liquefied gas+gasoline+diesel oil+oil fuel diesel and gasoline ratio propene yield | 77.38 57.36 84.91 0.52 11.21 | 76.50 58.68 84.28 0.52 8.27 |
Table 3
| Gasoline | Embodiment | 1 | Comparative Examples 1 |
| Density (20 ℃), g/cm
3Vapour pressure, Kpa colloid, mg/100ml |
0.7169 62 3 35 43 51.5 64.5 91.5 143.5 181 | 0.7109 63 3 39.0 51.0 64.0 87.0 122.0 161.0 184.0 | |
| Octane value RON MON group composition (chromatogram) alkane, (V) % alkene, (V) % aromatic hydrocarbons, (V) % | 93.1 81.2 30.7 31.4 37.9 | 93.6 81.2 33.3 45.9 30.8 |
Table 4
Table 5
Claims (3)
1. method that reduces olefin(e) centent in the high olefin gasoline, it is characterized in that: the gasoline of high olefin content is entered in the rectifying tower, cut in rectifying tower, the higher relatively light gasoline fraction of olefin(e) centent is isolated on tower top, and the tower still is the lower cut of olefin(e) centent; Tower top light gasoline fraction is again by MGD Technology, MIP Technology, directly be recycled into riser reactor middle part or adopt any technology in the FDFCC Technology to carry out upgrading; The heavy naphtha that the tower still is extracted out goes to follow-up workshop section to handle after being in harmonious proportion with the gasoline of crossing through secondary reaction more in the lump.
2, method according to claim 1 is characterized in that the rectifying tower tower top temperature is: 50 ℃～110 ℃, tower still temperature is: 120 ℃～160 ℃.
3, method according to claim 1 and 2, the gasoline that it is characterized in that high olefin content are selected from a kind of in catalytically cracked gasoline, coker gasoline, the pyrolysis gasoline or their mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410022857XA CN100451091C (en) | 2004-01-17 | 2004-01-17 | Method for reducing the content of olefin in high olefin gasoline |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410022857XA CN100451091C (en) | 2004-01-17 | 2004-01-17 | Method for reducing the content of olefin in high olefin gasoline |
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| Publication Number | Publication Date |
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| CN1557916A CN1557916A (en) | 2004-12-29 |
| CN100451091C true CN100451091C (en) | 2009-01-14 |
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| CNB200410022857XA Expired - Lifetime CN100451091C (en) | 2004-01-17 | 2004-01-17 | Method for reducing the content of olefin in high olefin gasoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102453516A (en) * | 2010-10-27 | 2012-05-16 | 中国石油化工股份有限公司 | Method for catalytically converting hydrocarbon oil with single lifting pipe |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973790A (en) * | 1989-11-16 | 1990-11-27 | Mobil Oil Corporation | Process for upgrading light olefinic streams |
| CN1458226A (en) * | 2002-05-13 | 2003-11-26 | 石油大学(北京) | Method and device for simple catalytic cracking sasoline modifincation and olefine reducing |
| CN1465664A (en) * | 2002-07-04 | 2004-01-07 | 石油大学(北京) | Method and system for reducing olefinic hydrocarbon content of catalytically cracked gasoline |
-
2004
- 2004-01-17 CN CNB200410022857XA patent/CN100451091C/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4973790A (en) * | 1989-11-16 | 1990-11-27 | Mobil Oil Corporation | Process for upgrading light olefinic streams |
| CN1458226A (en) * | 2002-05-13 | 2003-11-26 | 石油大学(北京) | Method and device for simple catalytic cracking sasoline modifincation and olefine reducing |
| CN1465664A (en) * | 2002-07-04 | 2004-01-07 | 石油大学(北京) | Method and system for reducing olefinic hydrocarbon content of catalytically cracked gasoline |
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| CN1557916A (en) | 2004-12-29 |
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