CN103396833B - A kind of synthetic naphtha produces the method for motor spirit - Google Patents
A kind of synthetic naphtha produces the method for motor spirit Download PDFInfo
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- CN103396833B CN103396833B CN201310370081.XA CN201310370081A CN103396833B CN 103396833 B CN103396833 B CN 103396833B CN 201310370081 A CN201310370081 A CN 201310370081A CN 103396833 B CN103396833 B CN 103396833B
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Abstract
The invention discloses a kind of method that synthetic naphtha produces motor spirit, comprise the steps: ICL for Indirect Coal Liquefaction technique synthetic naphtha to send into separation column fractionation, the C5-C6 that tower one line fractionates out sends into normal paraffin hydro-isomerization metallization processes and processes; Obtain at the bottom of tower >=80 DEG C of cuts send into fixed-bed catalytic reforming process and process; Send into degassing tower after the generation oil mixing finally normal paraffin hydro-isomerization metallization processes and fixed-bed catalytic reforming process obtained degassed, at the bottom of tower, obtain motor spirit component.The inventive method adopt fixed-bed catalytic reforming process by synthetic naphtha >=the C7-C9 alkane transformations of 80 DEG C becomes aromatic hydrocarbons; Normal paraffin hydro-isomerization metallization processes is adopted to realize the hydrocarbon isomerization of the C5-C6 normal paraffin in synthetic naphtha.The octane value of effective raising synthetic naphtha, produces the motor spirit that index reaches " national gasoline quality standard-VI ".
Description
One, technical field
The invention belongs to motor spirit production technical field, the method for motor spirit produced by the petroleum naphtha being specifically related to the synthesis of a kind of ICL for Indirect Coal Liquefaction technique.
Two, background technology
In China's ICL for Indirect Coal Liquefaction production technology, synthetic naphtha is the product of synthesis cold-trap oil after hydrogenation technique, and be that one of main products in synthetic oil is produced in gelatin liquefaction, its output accounts for 22% of product coal synthetic oil total recovery.Owing to generating a large amount of single diolefins in coal liquifaction technological process, this part alkene is changing into normal paraffin after hydrotreated lube base oil, and in product synthetic naphtha, normal paraffin content is generally about 85%.The octane value of normal paraffin is lower, and the octane value (RON) of nC6 is the octane value (RON) of 26, nC7 is 0.A large amount of existence of normal paraffin affect the octane value of synthetic naphtha lower than 40, and cannot dispatch from the factory as gasoline products, to coal liquifaction, manufacturing enterprise creates negative impact.Do not have ripe production technique can solve the too low problem of synthetic naphtha octane value at present both at home and abroad.Synthetic naphtha octane value is too low as motor spirit composition problems, can not become the bottleneck that coal liquifaction enterprise produces.Objectively existing coal liquifaction enterprise of China mostly concentrates the remote districts being based upon rich coal resources, communications and transportation difficulty, petrochemical complex derived product scarce capacity, and synthetic naphtha can not be given prominence to as this negative issue of motor spirit component is more aobvious.
Three, summary of the invention
The object of this invention is to provide a kind of method that ICL for Indirect Coal Liquefaction technique synthetic naphtha prepares motor spirit, adopt the method effectively can improve the octane value of synthetic naphtha, solve the problem that synthetic naphtha octane value is too low, produce the motor spirit that index reaches " national gasoline quality standard-VI ", solve coal liquifaction enterprise production technology bottleneck problem, improve coal liquifaction enterprise overall economic benefit.
For achieving the above object, the technical solution used in the present invention is: the method comprises the steps: ICL for Indirect Coal Liquefaction technique synthetic naphtha to send into separation column fractionation, tower top deviates from≤and the component of C4; The C5-C6 that tower one line fractionates out sends into normal paraffin hydro-isomerization metallization processes and processes; Obtain at the bottom of tower >=80 DEG C of cuts send into fixed-bed catalytic reforming process and process; Send into degassing tower after the generation oil mixing finally normal paraffin hydro-isomerization metallization processes and fixed-bed catalytic reforming process obtained degassed, at the bottom of tower, obtain motor spirit component.
The inventive method improves the octane value of synthetic naphtha, is realize when carbon number distribution is substantially constant.Adopt fixed-bed catalytic reforming process by synthetic naphtha >=the C7-C9 alkane transformations of 80 DEG C becomes aromatic hydrocarbons; Normal paraffin hydro-isomerization metallization processes is adopted to realize the hydrocarbon isomerization of the C5-C6 normal paraffin in synthetic naphtha.The octane value of effective raising synthetic naphtha, produces the motor spirit that index reaches " national gasoline quality standard-VI ", solves coal liquifaction enterprise production technology bottleneck problem, improves coal liquifaction enterprise overall economic benefit.
The present invention has following features:
1, have employed front fractionation process and first synthetic naphtha is isolated C5-C6 cut and >=80 DEG C of cuts, and have employed normal paraffin hydro-isomerization metallization processes and fixed-bed catalytic reformation combination process targetedly, respectively normal alkane isomerization and catalytic reforming aromatization are carried out to C5-C6 cut and >=80 DEG C of cuts, retained simultaneously making octane value active principle in synthetic naphtha, conflicting composition is changed into respectively the higher component of corresponding octane value, thus the overall octane value of synthetic naphtha is improved, reach motor spirit quality standard.
2, the inventive method adopts selectivity isomerization technique for nC5-nC6 cut; not only solve nC5-nC6 and affect the low problem of octane value; and due to isomerization gasoline susceptibility little (usual RON and MON only differs 1.5 units), the octane value adopting normal paraffin hydro-isomerization metallization processes to improve gasoline has realistic meaning to strengthen environmental protection.
4, because current reforming reaction can only improve the quality of 80-180 DEG C of part petroleum naphtha, and normal paraffin hysomer process adjustments front end≤80 DEG C gasoline component octane values, the generation oil of catalytic reforming and isomerization combination process, gasoline boiling range can be made to have more reasonably distribute, thus improve petrolic startability and improve active power.
5, ICL for Indirect Coal Liquefaction technique synthetic naphtha is reduced further through processing rear impurity content, and oil quality all reaches state IV gasoline standard requirement.
Four, embodiment
The present embodiment adopt the main physico-chemical property of ICL for Indirect Coal Liquefaction technique synthetic naphtha as following table:
The concrete steps of the inventive method are as follows
1. raw material pretreatment process:
ICL for Indirect Coal Liquefaction technique synthetic naphtha is sent into separation column, and tower top deviates from≤component of C4, and tower one line fractionates out C5-C6 cut as normal paraffin normal paraffin hysomer process feeds, obtain at the bottom of tower >=80 DEG C of cuts are as the charging of fixed bed reforming process.
2. normal paraffin hydro-isomerization metallization processes:
After the C5-C6 cut that tower one line is fractionated out and hydrogen Hybrid Heating to 250-270 DEG C of temperature of reaction, enter fixed bed isomerization reactor and carry out isomerization reaction under catalyst action, obtaining generating oil.
The catalyzer that above-mentioned normal paraffin hydro-isomerization metallization processes adopts is domestic FI-15 alkane isomerization catalyst.This catalyzer take molecular sieve as support of the catalyst, and Ni-Mo metal is Primary Catalysts and promotor.Catalyzer Main Function is the isomerization realizing nC5-nC6 normal paraffin, and for preventing having cracking side-reaction to occur in conversion process, reaction process needs to carry out facing under hydrogen state, and because hydrogen dividing potential drop does not need too high, reactive hydrogen oil ratio requires lower.
Above-mentioned normal paraffin hysomer technological reaction condition is:
Temperature (DEG C): 250-270 pressure (MPa): 1.5-2.0
Air speed (H
-1): 0.2-1.8 hydrogen-oil ratio (v/v): (1.5-5)/1
3. fixed-bed catalytic reforming process:
By obtaining at the bottom of tower >=80 DEG C of cuts are heated to after 470-520 DEG C of temperature of reaction mix with the hot hydrogen of relevant temperature, enter one section of fixed-bed catalytic reforming reactor and carry out catalytic reforming reaction, after gained one section of reforming reaction product and hydrogen mixture heat, enter two sections of fixed-bed catalytic reforming reactors and carry out second segment catalytic reforming reaction, after gained two sections of reformates and hydrogen mixture heat, enter three-section fixed-bed catalytic reforming reactor again and carry out reforming reaction, above-mentioned reaction all runs under catalyst action, finally obtains generating oil.
Above-mentioned fixed-bed catalytic reforming reactor quantity is four, and three reactor operation during normal production run, one uses for during catalyst regeneration.
Above-mentioned fixed-bed catalytic reforming process is strong endothermic reaction process, because of endothermic heat of reaction generation temperature drop by a relatively large margin in reaction process, the capacity scale of reactor is subject to temperature drop impact can not be excessive, between each fixed-bed catalytic reforming reactor, will heating facility be set, ensure that heat supply is sufficient to adjust flexibly with reactor inlet temperature, meet the demand that each reactor catalyst bed temperature all runs under required state.
The catalyzer that above-mentioned fixed-bed catalytic reforming process adopts is domestic PS-VI noble-metal reforming catalyst, and this catalyzer is with 5A molecular sieve for carrier, and platinum, iridium precious metal are Primary Catalysts and the promotor of reactive behavior.
The reaction conditions of above-mentioned fixed-bed catalytic reforming process is:
Temperature (DEG C): 470-520 pressure (MPa): 0.3-1.3
Air speed (H
-1): 1-3.5 hydrogen-oil ratio (v/v): (800-1300)/1
4. oily degasification technique is generated:
Normal paraffin hydro-isomerization metallization processes and fixed-bed catalytic reforming process enter in the middle part of degassing tower after generating oil mixing, owing to occurring with scission reaction in catalytic reforming and isomerization reaction, non-condensable gas and solution gas is deviate from by top, the motor spirit component carrying device at the bottom of tower after degassed in tower.
Reaction generates the physico-chemical property of oil as following table:
Reaction generates oil and contrasts as following table with " national gasoline quality standard-VI " leading indicator:
As can be known from the above table, indirect liquefaction technique synthetic naphtha is after normal paraffin hydro-isomerization metallization processes and fixed-bed catalytic reforming process are reacted, foreign matter content reduces, octane value is improved significantly, gasoline main standard index that quality product reaches " national gasoline quality standard-VI ", gasoline component octane value susceptibility particularly through normal paraffin hydro-isomerization metallization processes is little, the gasoline produced is more reasonable on fraction distribution, can improve the startability of engine.
Claims (7)
1. synthetic naphtha produces the method for motor spirit, and the method comprises the steps: ICL for Indirect Coal Liquefaction technique synthetic naphtha to send into separation column fractionation, and tower top deviates from≤component of C4; The C5-C6 that tower one line fractionates out sends into normal paraffin hydro-isomerization metallization processes and processes; Obtain at the bottom of tower >=80 DEG C of cuts send into fixed-bed catalytic reforming process and process; Send into degassing tower after the generation oil mixing finally normal paraffin hydro-isomerization metallization processes and fixed-bed catalytic reforming process obtained degassed, at the bottom of tower, obtain motor spirit component.
2. a kind of synthetic naphtha according to claim 1 produces the method for motor spirit, it is characterized in that: the concrete steps of the method are:
1. raw material pretreatment process:
ICL for Indirect Coal Liquefaction technique synthetic naphtha is sent into separation column, and tower top deviates from≤component of C4, and tower one line fractionates out C5-C6 cut as normal paraffin normal paraffin hysomer process feeds, obtain at the bottom of tower >=80 DEG C of cuts are as the charging of fixed bed reforming process;
2. normal paraffin hydro-isomerization metallization processes:
After the C5-C6 cut that tower one line is fractionated out and hydrogen Hybrid Heating to 250-270 DEG C of temperature of reaction, enter fixed bed isomerization reactor and carry out isomerization reaction under catalyst action, obtaining generating oil;
3. fixed-bed catalytic reforming process:
By obtaining at the bottom of tower >=80 DEG C of cuts are heated to after 470-520 DEG C of temperature of reaction mix with the hot hydrogen of relevant temperature, enter one section of fixed-bed catalytic reforming reactor and carry out catalytic reforming reaction, after gained one section of reforming reaction product and hydrogen mixture heat, enter two sections of fixed-bed catalytic reforming reactors and carry out second segment catalytic reforming reaction, after gained two sections of reformates and hydrogen mixture heat, enter three-section fixed-bed catalytic reforming reactor again and carry out reforming reaction, above-mentioned reaction all runs under catalyst action, finally obtains generating oil;
4. oily degasification technique is generated:
Normal paraffin hydro-isomerization metallization processes and fixed-bed catalytic reforming process enter in the middle part of degassing tower after generating oil mixing, owing to occurring with scission reaction in catalytic reforming and isomerization reaction, non-condensable gas and solution gas is deviate from by top, the motor spirit component carrying device at the bottom of tower after degassed in tower.
3. a kind of synthetic naphtha according to claim 1 and 2 produces the method for motor spirit, it is characterized in that: the catalyzer that described normal paraffin hydro-isomerization metallization processes adopts is FI-15 alkane isomerization catalyst.
4. a kind of synthetic naphtha according to claim 1 and 2 produces the method for motor spirit, it is characterized in that: described normal paraffin hysomer technological reaction condition is:
Temperature: 250-270 DEG C pressure: 1.5-2.0MPa
Air speed: 0.2-1.8H
-1hydrogen to oil volume ratio: (1.5-5)/1.
5. a kind of synthetic naphtha according to claim 1 and 2 produces the method for motor spirit, it is characterized in that: the catalyzer that described fixed-bed catalytic reforming process adopts is PS-VI noble-metal reforming catalyst.
6. a kind of synthetic naphtha according to claim 1 and 2 produces the method for motor spirit, it is characterized in that: the reaction conditions of described fixed-bed catalytic reforming process is:
Temperature: 470-520 DEG C pressure: 0.3-1.3MPa
Air speed: 1-3.5H
-1hydrogen to oil volume ratio: (800-1300)/1.
7. a kind of synthetic naphtha according to claim 2 produces the method for motor spirit, it is characterized in that: step 3. middle fixed-bed catalytic reforming reactor quantity is four, and three reactor operation during normal production run, one uses for during catalyst regeneration.
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FR3014895B1 (en) * | 2013-12-17 | 2017-02-10 | Ifp Energies Now | CATALYTIC REFORMING PROCESS |
CN105861043B (en) * | 2016-06-14 | 2017-10-24 | 洛阳市科创石化科技开发有限公司 | A kind of naphtha produces the process of high-knock rating gasoline |
CN111925822A (en) * | 2020-07-17 | 2020-11-13 | 中科合成油工程有限公司 | Method for preparing high-octane gasoline and device for implementing method |
CN113234471A (en) * | 2021-06-24 | 2021-08-10 | 中国石油化工股份有限公司 | Naphtha reforming processing optimization process |
CN115717088B (en) * | 2021-08-27 | 2024-05-17 | 中国石油化工股份有限公司 | No. 75 coal-based aviation gasoline composition and preparation method thereof |
CN113956900A (en) * | 2021-11-04 | 2022-01-21 | 辽宁北方华锦五洲化工工程设计有限公司 | Based on C5C6Naphtha deep processing method and device for isomerization device |
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US4747933A (en) * | 1987-03-27 | 1988-05-31 | Uop Inc. | Isomerization unit with integrated feed and product separation facilities |
CN101397230A (en) * | 2007-09-28 | 2009-04-01 | 中国石油化工股份有限公司 | C5 and/or C6 alkane isomerization process |
CN101570698A (en) * | 2008-04-29 | 2009-11-04 | 中国石油化工股份有限公司 | Method for catalyzing and transforming naphtha |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4747933A (en) * | 1987-03-27 | 1988-05-31 | Uop Inc. | Isomerization unit with integrated feed and product separation facilities |
CN101397230A (en) * | 2007-09-28 | 2009-04-01 | 中国石油化工股份有限公司 | C5 and/or C6 alkane isomerization process |
CN101570698A (en) * | 2008-04-29 | 2009-11-04 | 中国石油化工股份有限公司 | Method for catalyzing and transforming naphtha |
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