CN1277907C - Recombinant processing method for naphtha - Google Patents

Recombinant processing method for naphtha Download PDF

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CN1277907C
CN1277907C CN 200310113733 CN200310113733A CN1277907C CN 1277907 C CN1277907 C CN 1277907C CN 200310113733 CN200310113733 CN 200310113733 CN 200310113733 A CN200310113733 A CN 200310113733A CN 1277907 C CN1277907 C CN 1277907C
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petroleum naphtha
naphtha
treatment process
oil
ethene
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CN1621497A (en
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丁冉峰
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JINWEIHUI ENGINEERNIG TECHNOLOGY Co Ltd BEIJING
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JINWEIHUI ENGINEERNIG TECHNOLOGY Co Ltd BEIJING
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Abstract

The present invention discloses a naphtha recombination processing method. The method comprises the following steps: (1) naphtha is extracted and divided into residual oil and extracted oil; (2) the residual oil enters an ethene steam cracking device to be cracked; (3) the extracted oil enters a reforming device to be reformed. Compared with the prior art, the naphtha recombination processing method has the advantages that the yield of arene can be enhanced by more than 30%, and the yield of ethene can be enhanced by more than 40%.

Description

A kind of petroleum naphtha reorganization treatment process
Technical field
The present invention relates to a kind of petroleum naphtha reorganization treatment process, particularly a kind of petroleum naphtha reorganization treatment process that can improve ethene and aromatics yield.
Background technology
The ability of aromatic hydrocarbons and ethylene producing device and output thereof are one of topmost signs of petrochemical industry developmental level.
Mainly from the catalytic reforming and the extraction plant thereof of petroleum refining industry, the generation oil of reformer obtains Organic Chemicals aromatic hydrocarbons such as benzene, toluene and dimethylbenzene etc. by extraction to aromatic hydrocarbons, and this generates oil and also can directly mix with gasoline as antiknock component.Along with the development of development and national economy and petrochemical industry, the demand of aromatic hydrocarbons is sharply increased, thereby to the also corresponding increase of demand of reformed oil.
Be to solve the problems referred to above at present, not only invest greatly but increase catalytic reforming unit, and be subjected to its quantitative limitation that processes raw material by increasing the catalytic reforming production equipment.The raw material of catalytic reforming mainly is a petroleum naphtha, and petroleum naphtha mainly often reduces pressure to cut by crude oil and obtains.The content of petroleum naphtha in the output object of crude oil is limited, therefore in order to increase the output of petroleum naphtha, must the corresponding amount of finish that increases crude oil, can cause the excessive of gasoline and diesel oil, make the contradiction of petroleum products unreasonable structure of petrol and diesel oil surplus more outstanding.Because the arene underwater content in the petroleum naphtha is limited, generally only is about 40%, even increase the severity of catalytic reforming operation, aromatics conversion rate is also limited; And the over-drastic severe condition also can make scission reaction aggravation, and split product increases, and then causes liquid yield to reduce.
Ethene mainly obtains by the ethene steam cracking device, and its main raw material also is a petroleum naphtha.In order to improve ethylene yield, prior art is by improving the transformation efficiency that cracking temperature improves ethene.Owing to be subjected to the restriction of feedstock property, improve ethylene yield by increasing the naphtha cracking temperature, can cause tube coking, the ethene steam cracking device can't normally be moved.
Summary of the invention
The purpose of this invention is to provide a kind of petroleum naphtha reorganization treatment process that can increase substantially aromatic production, yield of ethene and liquid yield.
For achieving the above object, the present invention takes following technical scheme:
A kind of petroleum naphtha reorganization treatment process, its step is as follows: (1) carries out extracting and separating with petroleum naphtha earlier, isolates to raffinate oil and extract oil out; (2) raffinate oil and enter the ethene steam cracking device; (3) extract oil out and enter reformer.
A kind of optimal technical scheme is characterized in that: described petroleum naphtha can be virgin naphtha, coking hydrotreated naphtha, thermally splitting hydrotreated naphtha, hydrocracking petroleum naphtha or hydrofining petroleum naphtha.
A kind of optimal technical scheme is characterized in that: the heater outlet temperature of ethene steam cracking device is 700~950 ℃ described in the described step (2), and the residence time is 0.15-0.25 second, and the dilution steam generation ratio is 0.25~0.6.
A kind of optimal technical scheme is characterized in that: the temperature of reaction of reformer is 380-550 ℃ described in the described step (3), and reaction pressure is 0.1MPa~4.0MPa, and air speed is 0.1-10h -1, the hydrogen weight of oil is than being 1-100.
A kind of optimal technical scheme is characterized in that: extracting and separating solvent for use described in the described step (1) is dimethyl sulfoxide (DMSO), tetramethylene sulfone, N-Methyl pyrrolidone, N-formyl morpholine, Tetraglycol 99, second cyanogen.
A kind of optimal technical scheme is characterized in that: the solvent ratio of extracting and separating solvent for use is 1 described in the described step (1): 1-20: 1, and service temperature is 20~180 ℃, working pressure is 0.1~2.0MPa, solvent comprises water 0.1~12% (Wt.).
A kind of optimal technical scheme is characterized in that: the solvent ratio of extracting and separating solvent for use is 8: 1 described in the described step (1).
Described petroleum naphtha can be paraffinic base petroleum naphtha, intermediate base petroleum naphtha, cycloalkyl petroleum naphtha.
The extraction solvent for use can be sulfone class such as tetramethylene sulfone, glycols such as Tetraglycol 99 and five glycol, and alkane ketone such as N-Methyl pyrrolidone, amides and amine etc. also can two or more solvent use.
Because naphthenic hydrocarbon very easily dehydrogenation is converted into aromatic hydrocarbons, its transformation efficiency height, conversion process condition relax, conversion rate is fast; Alkane is very easily cracking then, generates ethene, and its transformation efficiency height, reaction conditions relax, conversion rate is fast.In original cracking of ethylene and the reforming process,, all can't under optimal conditions, transform because naphthenic hydrocarbon and alkane in the petroleum naphtha mix.Based on this, the present invention adopts abstraction technique, earlier petroleum naphtha is carried out extracting and separating, is separated into based on the oily component of the extraction of aromatic hydrocarbons and naphthenic hydrocarbon with based on the component of raffinating oil of alkane.The component of raffinating oil advances the cracking of ethene steam cracking device; Extract oily component out and advance the reformer reaction.Because extracting oily component out is good aromatic hydrocarbons raw materials for production, than under the low reaction temperatures, promptly can finish conversion, has improved aromatics conversion rate and liquid yield greatly.Same reformer, its aromatic production can improve more than 30%.Alkane component content is that raffinating oil of 80-95% is good ethene steam crack material, can improve yield of ethene under the identical operations condition, reduces the coke cleaning time of pyrolyzer simultaneously.Same ethene steam cracking device after employing the inventive method, can improve ethylene yield more than 40%.
Description of drawings
Fig. 1 advances the schematic flow sheet of reformer for petroleum naphtha;
Fig. 2 advances the schematic flow sheet of ethene steam cracking device for petroleum naphtha;
Fig. 3 is the schematic flow sheet of petroleum naphtha reorganization treatment process of the present invention.
Equipment component in the accompanying drawing such as reactor, compressor, pyrolyzer, separating tank, pump, various cold exchange devices etc. do not mark, but this is known to those of ordinary skills.
The present invention will be further described below by embodiment, but and do not mean that limiting the scope of the invention.
Embodiment
Comparative Examples 1
As shown in Figure 1, with density is that 735 kilograms per cubic meter, 80~165 ℃ of boiling range scopes, alkane content are that 56% (Wt.), naphthene content are that 41% (Wt.), aromaticity content are that the petroleum naphtha of 3% (Wt.) is through pre-treatment, enter the fixed-bed reactor reaction of the CB-5 reforming catalyst that Chang Ling catalyst plant production is housed, inlet amount is 100ml/h, obtain the reforming reaction product, its reaction conditions, aromatics yield and hydrogen yield see Table 1.
Comparative Examples 2
As shown in Figure 2, with density is that 735 kilograms per cubic meter, 80~165 ℃ of boiling range scopes, alkane content are that 56% (Wt.), naphthene content are that 41% (Wt.), aromaticity content are that the petroleum naphtha of 3% (Wt.) is through pre-treatment, enter the ethene steam cracking furnace, inlet amount is 100ml/h, and its reaction conditions, yield of ethene and cracking furnace pipe coke cleaning time see Table 2.
Embodiment 1
As shown in Figure 3, with density is that 735 kilograms per cubic meter, 80~165 ℃ of boiling range scopes, alkane content are that 56% (Wt.), naphthene content are that 41% (Wt.), aromaticity content are that the petroleum naphtha of 3% (Wt.) enters extraction plant, inlet amount is 2 kilograms/hour, solvent for use is a N-Methyl pyrrolidone, solvent comprises water 3% (Wt.), solvent ratio is 8: 1 (Wt.), and service temperature is 120 ℃, and working pressure is 0.6MPa; The flow of raffinating oil is that 1.15 kilograms/hour, density are that 667 kilograms per cubic meter, boiling range scope are 80~163 ℃, consists of alkane 95.40% (Wt.), naphthenic hydrocarbon 4.42% (Wt.), aromatic hydrocarbons 0.18% (Wt.); The flow of extracting oil out is that 0.85 kilogram/hour, density are that 798 kilograms per cubic meter, boiling range scope are 80~168 ℃, consists of alkane 2.36% (Wt.), naphthenic hydrocarbon 90.80% (Wt.), aromatic hydrocarbons 6.84% (Wt.).Gained is raffinated oil and is entered ethene steam cracking furnace in the Comparative Examples 2; Gained is extracted the oily reformer that enters in the Comparative Examples 1 out.Its reaction conditions and aromatics yield, hydrogen yield, yield of ethene and pyrolyzer coke cleaning time see Table 1 and table 2.
Table 1
Comparative Examples 1 Embodiment 1 Change
Temperature of reaction, ℃ 510 465 45
Reaction pressure, MPa 1.0 1.0 0
Air speed, h -1 2.0 2.0 0
Hydrogen/oil mol ratio 2.98 2.98 0
Hydrogen yield, % (Wt.) 2.74 4.48 +1.74
Aromatics yield, % (Wt.) 50.13 92.15 +42.02
By table 1 as seen, compare with Comparative Examples 1, the petroleum naphtha reorganization treatment process of embodiments of the invention 1, its reorganization back hydrogen yield has improved nearly 2 percentage points, and aromatics yield has improved 42%.
Table 2
Comparative Examples 2 Embodiment 1 Change
Heater outlet temperature, ℃ 840 840 0
The residence time, s 0.2 0.2 0
Outlet of still pressure, MPa 0.17 0.17 0
The dilution steam generation ratio 0.32 0.32 0
The cracking furnace pipe coke cleaning time, day 50 100 +50
Yield of ethene, % (Wt.) 28 43 +15
By table 2 as seen, compare with Comparative Examples 2, the petroleum naphtha of embodiments of the invention 1 reorganization treatment process gained yield of ethene has improved 15 percentage points, pyrolyzer coke cleaning time lengthening one times.
Comparative Examples 3
With density is that 724 kilograms per cubic meter, 70~171 ℃ of boiling range scopes, alkane content are that 65% (Wt.), naphthene content are that 31% (Wt.), aromaticity content are that the petroleum naphtha of 4% (Wt.) is through pre-treatment, enter the fixed-bed reactor reaction of the CB-5 reforming catalyst that Chang Ling catalyst plant production is housed, inlet amount is 100ml/h, obtain the reforming reaction product, its reaction conditions, aromatics yield and hydrogen yield see Table 3.
Comparative Examples 4
With density is that 724 kilograms per cubic meter, 70~171 ℃ of boiling range scopes, alkane content are that 65% (Wt.), naphthene content are that 31% (Wt.), aromaticity content are that the petroleum naphtha of 4% (Wt.) is through pre-treatment, enter the ethene steam cracking furnace, inlet amount is 100ml/h, get the reaction product of ethene steam cracking, its reaction conditions, yield of ethene and cracking furnace pipe coke cleaning time see Table 4.
Embodiment 2
With density is that 724 kilograms per cubic meter, 70~171 ℃ of boiling range scopes, alkane content are that 65% (Wt.), naphthene content are that 31% (Wt.), aromaticity content are that the petroleum naphtha of 4% (Wt.) enters extraction plant, inlet amount is 2 kilograms/hour, solvent for use is a dimethyl sulfoxide (DMSO), solvent comprises water 5% (Wt.), the weight of solvent ratio is 7: 1, service temperature is 95 ℃, and working pressure is 0.7MPa; The flow of raffinating oil is 1.332 kilograms/hour, and density is 695 kilograms per cubic meter, and the boiling range scope is 68~163 ℃, consists of alkane 96.10% (Wt.), naphthenic hydrocarbon 3.75% (Wt.), aromatic hydrocarbons 0.15% (Wt.).The flow of extracting oil out is 0.668 kilogram/hour, and density is 789 kilograms per cubic meter, and the boiling range scope is 71~168 ℃, consists of alkane 3.00% (Wt.), naphthenic hydrocarbon 85.33% (Wt.), aromatic hydrocarbons 11.68% (Wt.).Gained is raffinated oil and is entered ethene steam cracking furnace in the Comparative Examples 4; Gained is extracted the oily reformer that enters in the Comparative Examples 3 out.Its reaction conditions and aromatics yield, hydrogen yield, yield of ethene and pyrolyzer coke cleaning time see Table 3 and table 4.
Table 3
Comparative Examples 3 Embodiment 2 Change
Temperature of reaction, ℃ 510 465 45
Reaction pressure, Mpa 1.0 1.0 0
Air speed, h -1 2.0 2.0 0
Hydrogen/oil mol ratio 2.98 2.98 0
Hydrogen yield, % (Wt.) 2.24 4.05 +1.81
Aromatics yield, % (Wt.) 50.13 90.83 +40.70
By table 3 as seen, compare with Comparative Examples 3, the petroleum naphtha reorganization treatment process of embodiments of the invention 2, its reorganization back hydrogen yield has improved nearly 2 percentage points, and aromatics yield has improved more than 40%.
Table 4
Comparative Examples 4 Embodiment 2 Change
Heater outlet temperature, ℃ 830 830 0
The residence time, s 0.2 0.2 0
Outlet of still pressure, MPa 0.17 0.17 0
The dilution steam generation ratio 0.32 0.32 0
The cracking furnace pipe coke cleaning time, day 45 100 +55
Yield of ethene, % (Wt.) 29 42 +13
By table 4 as seen, compare with Comparative Examples 4, the petroleum naphtha of embodiments of the invention 2 reorganization treatment process gained yield of ethene has improved 13 percentage points, pyrolyzer coke cleaning time lengthening more than one times.
Comparative Examples 5
With density is that 738 kilograms per cubic meter, 75~172 ℃ of boiling range scopes, alkane content are that 39.5% (Wt.), naphthene content are that 55.3% (Wt.), aromaticity content are that the petroleum naphtha of 5.2% (Wt.) is through pre-treatment, enter the fixed-bed reactor reaction of the CB-5 reforming catalyst that Chang Ling catalyst plant production is housed, inlet amount is 100ml/h, obtain the reforming reaction product, its reaction conditions, aromatics yield and hydrogen yield see Table 5.
Comparative Examples 6
With density is that 738 kilograms per cubic meter, 75~172 ℃ of boiling range scopes, alkane content are that 39.5% (Wt.), naphthene content are that 55.3% (Wt.), aromaticity content are that the petroleum naphtha of 5.2% (Wt.) is through pre-treatment, enter the ethene steam cracking furnace, inlet amount is 100ml/h, get the reaction product of ethene steam cracking, its reaction conditions, yield of ethene and cracking furnace pipe coke cleaning time see Table 6.
Embodiment 3
With density is that 738 kilograms per cubic meter, 75~172 ℃ of boiling range scopes, alkane content are that 39.5% (Wt.), naphthene content are that 55.3% (Wt.), aromaticity content are that the petroleum naphtha of 5.2% (Wt.) enters extraction plant, inlet amount is 2 kilograms/hour, solvent for use is a tetramethylene sulfone, solvent comprises water 0.5% (Wt.), the weight of solvent ratio is 11: 1, service temperature is 128 ℃, and working pressure is 1.0MPa; The flow of raffinating oil is 0.83 kilogram/hour, and density is 688 kilograms per cubic meter, and the boiling range scope is 73~170 ℃, consists of alkane 93.98% (Wt.), naphthenic hydrocarbon 4.82% (Wt.), aromatic hydrocarbons 1.20% (Wt.).The flow of extracting oil out is 1.17 kilograms/hour, and density is 793 kilograms per cubic meter, and the boiling range scope is 71~174 ℃, consists of alkane 0.85% (Wt.), naphthenic hydrocarbon 91.11% (Wt.), aromatic hydrocarbons 8.04% (Wt.).Gained is raffinated oil and is entered ethene steam cracking furnace in the Comparative Examples 6; Gained is extracted the oily reformer that enters in the Comparative Examples 5 out.Its reaction conditions and aromatics yield, hydrogen yield, yield of ethene and pyrolyzer coke cleaning time see Table 5 and table 6.
Table 5
Comparative Examples 5 Embodiment 3 Change
Temperature of reaction, ℃ 510 465 45
Reaction pressure, MPa 1.0 1.0 0
Air speed, h -1 2.0 2.0 0
Hydrogen/oil mol ratio 2.98 2.98 0
Hydrogen yield, % (Wt.) 2.87 4.42 +1.55
Aromatics yield, % (Wt.) 55.2 93.84 +38.64
By table 5 as seen, compare with Comparative Examples 5, the petroleum naphtha reorganization treatment process of embodiments of the invention 3, its reorganization back hydrogen yield has improved 1.55 percentage points, and aromatics yield has improved 39%.
Table 6
Comparative Examples 6 Embodiment 3 Change
Heater outlet temperature, ℃ 850 850 0
The residence time, s 0.2 0.2 0
Outlet of still pressure, MPa 0.17 0.17 0
The dilution steam generation ratio 0.32 0.32 0
The cracking furnace pipe coke cleaning time, day 48 120 +72
Yield of ethene, % (Wt.) 24 45 +21
By table 6 as seen, compare with Comparative Examples 6, the petroleum naphtha of embodiments of the invention 3 reorganization treatment process gained yield of ethene has improved 21 percentage points, pyrolyzer coke cleaning time lengthening 72 days.
Petroleum naphtha, alkane, the naphthene content raffinating oil, extract out in the oil are tested with the GB11132-2002 method; Petroleum naphtha, the density GB/T1884-1885 method test of raffinating oil, extracting out oil; Petroleum naphtha, the boiling range scope GB/T6536 method test of raffinating oil, extracting out oil.

Claims (7)

1, a kind of petroleum naphtha reorganization treatment process, its step is as follows: (1) carries out extracting and separating with petroleum naphtha earlier, isolates to raffinate oil and extract oil out; (2) the into ethene steam cracking device of raffinating oil; (3) extract oil out and advance reformer; The extracting and separating solvent for use is dimethyl sulfoxide (DMSO), tetramethylene sulfone, N-Methyl pyrrolidone or Tetraglycol 99 described in the described step (1); The solvent ratio of extracting and separating solvent for use is 1: 1~20: 1 described in the described step (1), and service temperature is 20~180 ℃, and working pressure is 0.1~2.0MPa, solvent comprises water 0.1~12 weight %.
2, petroleum naphtha reorganization treatment process according to claim 1, it is characterized in that: described petroleum naphtha is virgin naphtha, coking hydrotreated naphtha, thermally splitting hydrotreated naphtha, hydrocracking petroleum naphtha or hydrofining petroleum naphtha.
3, according to each described petroleum naphtha reorganization treatment process in claim 1 or 2, it is characterized in that: the heater outlet temperature of ethene steam cracking device is 700~950 ℃ described in the described step (2), the residence time is 0.15~0.25 second, and the dilution steam generation ratio is 0.25~0.6.
4, according to each described petroleum naphtha reorganization treatment process in claim 1 or 2, it is characterized in that: the heater outlet temperature of ethene steam cracking device is 830~850 ℃ described in the described step (2), and the residence time is 0.2 second, and the dilution steam generation ratio is 0.32.
5, according to each described petroleum naphtha reorganization treatment process in claim 1 or 2, it is characterized in that: the temperature of reaction of reformer is 380~550 ℃ described in the described step (3), and reaction pressure is 0.1MPa~4.0MPa, and air speed is 0.1~10h -1, hydrogen weight of oil ratio is 1~100.
6, according to each described petroleum naphtha reorganization treatment process in claim 1 or 2, it is characterized in that: the temperature of reaction of reformer is 450~500 ℃ described in the described step (3), and reaction pressure is 0.2MPa~2.0MPa, and air speed is 1.0~5h -1, hydrogen weight of oil ratio is 1~3.
7, according to each described petroleum naphtha reorganization treatment process in claim 1 or 2, it is characterized in that: the solvent ratio of extracting and separating solvent for use is 7: 1~8: 1 described in the described step (1), service temperature is 90~100 ℃, working pressure is 1.0~1.5MPa, solvent comprises water 0.9~6 weight %.
CN 200310113733 2003-11-24 2003-11-24 Recombinant processing method for naphtha Expired - Fee Related CN1277907C (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101760356B1 (en) * 2013-03-05 2017-07-21 차이나 페트로리움 앤드 케미컬 코포레이션 A process of producing olefins and aromatic hydrocarbons

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CN101497806B (en) * 2008-01-29 2013-04-10 丁冉峰 System and method for preparing high quality petrol
CN101759513B (en) * 2008-12-25 2012-08-22 中国石油化工股份有限公司 Method for utilizing naphtha
EP2390303B1 (en) * 2009-01-21 2017-07-26 Beijing Grand Golden-Bright Engineering & Technologies Co., Ltd. Process for producing high quality gasoline by recombination and subsequent hydrogenation of catalytic hydrocarbons
CN102839021A (en) * 2011-06-22 2012-12-26 北京金伟晖工程技术有限公司 Device and method for preparing low-sulfur high-octane gasoline at low cost
CN102517072B (en) * 2011-12-16 2014-03-05 天津大学 Method and device for optimizing naphtha
CN104031680B (en) * 2013-03-05 2016-04-27 中国石油化工股份有限公司 A kind of method of being produced alkene and low benzene content gasoline by petroleum naphtha
CN104927919B (en) * 2014-03-18 2017-02-15 中国石油化工股份有限公司 Method for producing olefin and low-benzene-content gasoline component from naphtha
CN104927915B (en) * 2014-03-18 2017-01-25 中国石油化工股份有限公司 Method for producing olefins and aromatic hydrocarbons with naphtha as raw material

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KR101760356B1 (en) * 2013-03-05 2017-07-21 차이나 페트로리움 앤드 케미컬 코포레이션 A process of producing olefins and aromatic hydrocarbons

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