CN1091460C - Solvent refining and hydrocracking combined process for poor-quality wax oil - Google Patents
Solvent refining and hydrocracking combined process for poor-quality wax oil Download PDFInfo
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- CN1091460C CN1091460C CN98122189A CN98122189A CN1091460C CN 1091460 C CN1091460 C CN 1091460C CN 98122189 A CN98122189 A CN 98122189A CN 98122189 A CN98122189 A CN 98122189A CN 1091460 C CN1091460 C CN 1091460C
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Abstract
The present invention relates to a combined process for deeply processing poor-quality wax oil, the aldehyde of the refined oil and the extracted oil which are obtained after the poor-quality wax oil (secondary processing wax oil which comprises coking wax oil, thermal cracking wax oil and catalytic cracking cycle oil, and/or straight poor-quality distillation heavy wax oil with high nitrogen contents) is pre-refined by a solvent refining apparatus is removed by the gas lift of hydrocracking tail gas, or catalytic cracking dry gas, or C5 <-> gas or coking gas, a section of narrow fraction of the refined oil is mixed with a section of narrow fraction of extracted oil after gas lift and then enter a hydrocracking unit, wherein the temperature of each section of narrow fraction is lower than 500 DEG C. The process has the advantages that the high-quality raw material is provided for hydrocracking, the poisoning of hydrocracking catalysts is lightened, and the arene latent content of heavy naphtha is improved.
Description
The invention belongs to petrochemical industry, relate to a kind of technology of faulty wax oil deep processing.
Faulty wax oil comprises the straight run wax slop of the secondary processing wax oil inferior of wax tailings, thermally splitting wax oil, catalytic cracking recycle oil and high nitrogen, high-acid crude oil, and its common feature is to be rich in aromatic hydrocarbons, sulphur, nitrogen, is difficult to processing.At present, most refineries are incorporated into it to advance catalytic cracking unit processing in the straight-run gas oil, thereby make the lightweight oil productive rate of catalytic cracking unit reduce, and coking yield rises, the quality product variation, and cause the processing power of catalytic cracking unit to descend.The part refinery handles it with hydrogenation technique, but because it is rich in heavy arene, sulphur, nitrogen, difficulty of processing is very big.The refinery that also has is called in it in oil fuel, thereby has influenced the overall economic efficiency of refinery.
Around the reprocessing problem of faulty wax oil, the oil refining workers of various countries are all carrying out the work.Chinese patent CN1042730A proposes, and with solvent extraction and hydrofining combinations produce cracking ethylene raw material, its solvent extraction method is single solvent extraction.Chinese patent CN1176295A proposes, and with the refining faulty wax oil of solvent pairs method for extracting, the yield height of raffinating oil is extracted oily aromatic hydrocarbons purity height out, raffinates oil after hydrofining as the cracking ethylene raw material or as hydrocracking raw material.But, because the aromaticity content of raffinating oil is lower, cause the arene underwater content of hydrocracking heavy naphtha to descend, unfavorable to producing BTX, and when carrying with water vapor gas, the higher activity that can influence hydrogenation catalyst again of the aldehyde contenting amount of raffinating oil.
The object of the present invention is to provide a kind of faulty wax oil solvent treatment and hydrocracking combined process,, alleviate hydrocracking catalyst and poison, improve the arene underwater content of heavy naphtha for hydrocracking provides high quality raw material.
The objective of the invention is to realize by following proposal.
Faulty wax oil is after solvent treatment, and treated oil that obtains and extraction oil adopt hydrocracking tail gas or catalytic cracked dry gas or C
5 -Gas or coking gas gas are carried, and one section narrow fraction less than 500 ℃ in treated oil after gas is carried and the extraction oil mixes direct raw material as hydroeracking unit, or mix the raw material of back as hydroeracking unit with part high-quality straight-run gas oil.
Processing condition of the present invention are as follows:
The solvent treatment part:
Faulty wax oil, boiling range are 320～600 ℃, if wherein contain less than 320 ℃ of cuts, need give first flash distillation and remove it, to avoid solvent slop.Described faulty wax oil comprises the secondary processing wax oil inferior and/or the high straight run wax slop inferior of nitrogen content of wax tailings, thermally splitting wax oil and catalytic cracking recycle oil, or two or more mixing oil of above-mentioned wax oil.
Technology can be used double solvent extraction technology, also available single solvent treatment technology.
When adopting double solvent extraction technology, main solvent can be with wet furfural, phenol or the N-Methyl pyrrolidone of dried furfural, moisture 5～8m%.
The back suction solvent, 80～250 ℃ of available boiling ranges, aromaticity content are less than the lightweight oil of 5m%, and best boiling range is 100～200 ℃.Described lightweight oil is a reforming raffinate oil, 120
#Solvent oil, 200
#Solvent oil, tasteless kerosene.
Solvent ratio is a main solvent: raw material: back suction solvent=0.3～2.0: 1.0: 0.2～1.0 (weight ratios), optimum solvent is than being main solvent: raw material: back suction solvent=0.5～1.0: 1.0: 0.2～0.6 (weight ratio).
Solvent treatment tower temperature is 60～100 ℃ of cats head, in the tower 50～75 ℃, and at the bottom of the tower about 40 ℃.
When adopting single solvent treatment technology, solvent can be with wet furfural, phenol or the N-Methyl pyrrolidone of dried furfural, moisture 5～8% (weight).Solvent ratio is a solvent: raw material=0.3～2.0: 1.0 (weight ratios).
Solvent treatment tower temperature is 60～100 ℃ of cats head, in the tower 50～75 ℃, and at the bottom of the tower about 40 ℃.
Treated oil and the extraction of adopting above-mentioned single solvent treatment technology or double solvent extraction technology to obtain are oily with hydrocracking tail gas, catalytic cracked dry gas, C
5 -Gas or coking gas gas are carried, and gas temperature raising degree is 40～200 ℃, oil: gas=5～10: 1 (weight ratio).
The hydrocracking part:
Adopt the treated oil after above-mentioned solvent treatment part gas is carried and extract out in the oil less than one section narrow fraction of 500 ℃ and mix directly or mix laggard as raw material with part high-quality straight-run gas oil.
Hydrobon catalyst can be one or more catalyst for refining, and refining section hydrogen dividing potential drop is 8.0～15.0MPa, and temperature of reaction is 350～410 ℃, and weight hourly space velocity is 0.60～1.20h
-1, hydrogen to oil volume ratio is 800～2000: 1.
Hydrocracking section catalyzer can be one or more cracking catalyst, and cracking zone hydrogen dividing potential drop is 8.0～15.0MPa, and temperature of reaction is 350～410 ℃, and weight hourly space velocity is 1.0～2.0h
-1, hydrogen to oil volume ratio is 800～2000: 1.
The unusual effect that the present invention produces is: drop to below the 50 μ g/g about can making in treated oil and the extraction oil aldehyde by 180 μ g/g with gas extracting method of the present invention, like this, just can alleviate the poisoning of aldehyde to hydrocracking catalyst.To extract out in the oil, can make the arene underwater content of hydrocracking heavy naphtha improve 10 percentage points (comparing) with the hydrocracking heavy naphtha of only making raw material with treated oil less than one section narrow fraction of 500 ℃ part as hydrocracking raw material.Therefore, adopt technology of the present invention can effectively reach purpose of the present invention, produce significant technique effect.
Describe the present invention in detail below in conjunction with accompanying drawing, but accompanying drawing does not limit the present invention.
Fig. 1 is faulty wax oil solvent treatment of the present invention and hydrocracking combined process schematic flow sheet.
Faulty wax oil 1 advances the refining tower of solvent; Main solvent 2 is advanced on the refining tower top of solvent, and the bottom is advanced Back suction solvent 3; Refined liquid 4 is overflowed from the refining top of tower of solvent and is entered solvent recovery tower A, reclaims Enter air lift tower A behind the solvent, after hydrocracking tail gas 16 air lifts, obtain refined oil after the air lift 11, the main solvent 7 of recovery and the back suction solvent 6 that reclaims recycle; Extract is refining from solvent Tower bottom is emitted and is entered solvent recovery tower B, enters air lift tower B behind the recovery solvent, through hydrocracking After tail gas 16 air lifts, obtain extracting oil 12 out after the air lift main solvent 9 of recovery and the back suction that reclaims Solvent 8 recycles; Extract oil 12 out and enter fractionating column, obtain the one section narrow branch that heats up in a steamer less than 500 ℃ 13 and residue part extract oil 14 out; 10 is stripper overhead gas; Refined oil 11, to extract oil out medium and small Heat up in a steamer in 500 ℃ one section narrow and to enter the hydrocracking dress with straight-run gas oil 15 after branch 13 mixes Put, obtain light naphtha 17, heavy naphtha 18, light diesel fuel 19 and hydrocracking tail oil 20.
Be an exemplary embodiments of the present invention below.
(mixed weight is than being A: B=7: 3) for the mixing oil C of the straight run wax slop B of certain wax tailings A and certain high nitrogen, high-acid crude oil, adopt faulty wax oil solvent treatment of the present invention and hydrocracking combined process that mixing oil C is handled, obtain light naphthar, heavy naphtha, solar oil and hydrocracking tail oil.
Solvent-refined processing condition are, main solvent is the furfural of moisture 5% (weight), and the back suction solvent is 90～120 ℃ a lightweight oil, 80 ℃ for the treatment of tower head temperature, 40 ℃ of bottom temps, solvent ratio are main solvent: mixing oil C: back suction solvent=0.8: 1.0: 0.3 (weight ratio).Test is finished on the 48kg/d pilot plant, and the gas tower is carried with steam gas.Under these conditions, the yield of treated oil D is 80% (weight), and the yield of extracting oil out is 20% (weight), and purity reaches 98% (weight) (aromatic hydrocarbons+colloid), and the content of aldehyde all reaches 160 μ g/g in treated oil D and the extraction oil.Carry treated oil D and extract oil out with hydrocracking tail gas gas, its processing condition are: oil/gas 7.0/1.0 (weight ratio), gas temperature raising degree is 100 ℃.Extraction oil (320～400 ℃ of cuts) after the gas that mixes 15% (weight) among the treated oil D after gas is put forward is carried, form mixing oil E, furfural content among the mixing oil E is 50 μ g/g, meet the oxygen level requirement of hydrocracking charging, D compares with treated oil, can alleviate the poisoning to hydrocracking catalyst.The character of raw material, treated oil D and mixing oil E is listed in table-1.Treated oil D and mixing oil E are carried out the hydrocracking test respectively, its processing condition are, refining section and cracking zone are selected HC-K and 3825 catalyzer respectively for use, the hydrogen dividing potential drop is 15.0MPa, refining section and cracked temperature of reaction are respectively 380 ℃ and 375 ℃, and the weight hourly space velocity of refining section and cracking zone is respectively 0.9h
-1And 1.8h
-1, hydrogen to oil volume ratio is 1500: 1.Test is to finish on 100ml hydrocracking pilot plant, adopts the single hop series connection once to pass through flow process.Test-results sees Table-2.By table-1 with show-2 as can be seen, mixing oil C is after solvent treatment, and quality is able to obvious improvement, and mixing oil E is through after the hydrocracking, the arene underwater content of heavy naphtha is directly compared through the heavy naphtha that hydrocracking obtains with treated oil D, improves nearly 10 percentage point.
Table-1 raw material or treated oil A B C D E density, 20 ℃, kg/m
3908.1 930.0 920.0 880.0 889.1 sulphur, μ/g 2,600 2,800 2,700 1,800 1950 nitrogen, μ/g 6,300 3,500 5,000 1,400 1500 carbon residues, m% 0.21 0.55 0.28 0.12 0.15 forms, m% stable hydrocarbon 59.0 61.0 60.0 72.0 65.8 aromatic hydrocarbons+colloid 41.0 39.0 40.0 28.0 34.2 aldehyde, μ g/g 160 50 tables 2
Raw material D E product distributes (hydrocracking is generated oil), m%
＜65℃ 6.8 5.6
65～177℃ 30.0 28.0
177～350℃ 29.8 31.7
＞350 ℃ 23.4 34.7 heavy naphtha (65～177 ℃) aromatic hydrocarbons is dived and is contained 52.0 61.7 amounts, m% diesel oil (177～350 ℃) cetane value 50 48
Claims (6)
1, a kind of combination process of faulty wax oil deep processing comprises solvent treatment and hydrocracking two portions, faulty wax oil through solvent refining unit give refining after, the treated oil that obtains and extract oil out and adopt hydrocracking tail gas or catalytic cracked dry gas or C
5 -Gas or coking gas gas are carried, the treated oil after gas is carried and extract out in the oil to mix less than one section narrow fraction of 500 ℃ and enter hydroeracking unit after mix directly or with part high-quality straight-run gas oil the back.
2, combination process according to claim 1, it is characterized in that described faulty wax oil comprises the secondary processing wax oil inferior and/or the high straight run wax slop inferior of nitrogen content of wax tailings, thermally splitting wax oil, catalytic cracking recycle oil, or two or more mixing oil of above-mentioned wax oil.
3, combination process according to claim 1 and 2, it is characterized in that described solvent treatment technology is single solvent treatment technology, used solvent is wet furfural or phenol or the N-Methyl pyrrolidone of furfural or moisture 5～8 weight %, and the weight ratio of solvent is a solvent: raw material=0.3～2.0: 1.0.
4, combination process according to claim 1 and 2, it is characterized in that described solvent treatment technology is the double solvent extraction process for refining, used main solvent is wet furfural or phenol or the N-Methyl pyrrolidone of furfural or moisture 5～8 weight %, the back suction solvent adopts boiling range at 80～250 ℃, the aromaticity content lightweight oil less than 5 weight %, and weight of solvent is than being main solvent: raw material: back suction solvent=0.3～2.0: 1.0: 0.2～1.0.
5, combination process according to claim 4 is characterized in that described back suction solvent adopts boiling range at 100～200 ℃, the aromaticity content lightweight oil less than 5 weight %.
6,, it is characterized in that described lightweight oil is a reforming raffinate oil, 120 according to the described combination process of claim 5
#Solvent oil, 200
#Solvent oil, tasteless kerosene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122189A CN1091460C (en) | 1998-12-29 | 1998-12-29 | Solvent refining and hydrocracking combined process for poor-quality wax oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98122189A CN1091460C (en) | 1998-12-29 | 1998-12-29 | Solvent refining and hydrocracking combined process for poor-quality wax oil |
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| Publication Number | Publication Date |
|---|---|
| CN1243860A CN1243860A (en) | 2000-02-09 |
| CN1091460C true CN1091460C (en) | 2002-09-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN98122189A Expired - Fee Related CN1091460C (en) | 1998-12-29 | 1998-12-29 | Solvent refining and hydrocracking combined process for poor-quality wax oil |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348696C (en) * | 2003-12-17 | 2007-11-14 | 中国石油化工股份有限公司武汉分公司 | Coking petrolatum oil processing method |
| CN101955797A (en) * | 2010-10-22 | 2011-01-26 | 华东理工大学 | Method for inhibiting alkaline nitrides in coker gatch |
| CN104611031B (en) * | 2013-11-05 | 2017-02-08 | 中国石油化工股份有限公司 | Process method for maximally producing chemical industry raw material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042730A (en) * | 1989-09-11 | 1990-06-06 | 齐鲁石油化工公司研究院 | Utilize wax oil to produce the new technology of high-value product |
| CN1176295A (en) * | 1996-09-06 | 1998-03-18 | 中国石油化工总公司 | Double-solvant extraction for inferior paraffin base oil |
-
1998
- 1998-12-29 CN CN98122189A patent/CN1091460C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042730A (en) * | 1989-09-11 | 1990-06-06 | 齐鲁石油化工公司研究院 | Utilize wax oil to produce the new technology of high-value product |
| CN1176295A (en) * | 1996-09-06 | 1998-03-18 | 中国石油化工总公司 | Double-solvant extraction for inferior paraffin base oil |
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| CN1243860A (en) | 2000-02-09 |
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Owner name: CHINA PETROCHEMICAL CORPORATION 2001.8.4; LUOYANG Free format text: FORMER OWNER: CHINA PETROCHEMICAL CORPORATION; LUOYANG PETROCHEMICAL ENGINEERING CO., CHINA PETROCHEMICAL CORP. Effective date: 20010804 |
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Effective date of registration: 20010804 Applicant after: China Petrochemical Group Corp. Applicant after: Luoyang Petrochemical Engineering Co., China Petrochemical Group Applicant before: China Petrochemical Group Corp. Applicant before: Luoyang Petro-chemical Engineering Co., Ltd., Sinopec |
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