CN1163879A - Procedure for generating pure aromatics from reformed gasoline and device for implementing the procedure - Google Patents
Procedure for generating pure aromatics from reformed gasoline and device for implementing the procedure Download PDFInfo
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- CN1163879A CN1163879A CN 97102403 CN97102403A CN1163879A CN 1163879 A CN1163879 A CN 1163879A CN 97102403 CN97102403 CN 97102403 CN 97102403 A CN97102403 A CN 97102403A CN 1163879 A CN1163879 A CN 1163879A
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Abstract
The invention relates to method for producing pure arene by reformed gasoline. In first step, the reformed gasoline is selectively hydrogenated, wherein, hydrogenation condition is that main non-aromatics, especially olefin, diene and alkatriene, are hydrogenated. And then, in second step, the product containing arene and obtained by selective hydrogenation in the first step is separated into arene and non-aromatics by extractive distillation and/or liquid-liquid solvent extraction.
Description
The present invention relates to produce the method for pure aromatics by reformed gasoline.The invention still further relates to the device of this method of realization.Reformed gasoline is high in aromatics gasoline, and it is the reformation by crude oil fractions, particularly produces by the catalytic reforming of crude oil fractions.In reforming process, be alkane and naphthenic hydrocarbon generation isomerization, rearrangement, cyclisation, dehydrogenation and similarly reaction contained in the crude oil at oil.The rich aromatic hydrocarbons reformed gasoline of being produced by catalytic reforming is an important basic raw material of producing aromatic hydrocarbons.Aromatic hydrocarbons, especially benzene,toluene,xylene and ethylbenzene are chemical industry, particularly produce the important basic raw material of plastics and regenerated fiber.Aromatic hydrocarbons also is used as the octane enhancer of gasoline.Because the increase that chemical industry needs aromatic hydrocarbons is so design the used reaction conditions and the catalyzer of catalytic reforming of the crude oil fractions of high aromatics yield.But the result has also produced a large amount of undersaturated non-aromatics, particularly alkene.Yet chemical industry is needed mainly to be pure aromatics, promptly contains the aromatic hydrocarbons of a small amount of as far as possible undersaturated non-aromatics impurity.Up to now, these impurity that are made of undersaturated non-aromatics only may separate with aromatic hydrocarbons with the chemical separation method by the physics of complexity, and to remove non-aromatics fully generally be impossible.With bromine index and pickling chromatic number (Saurefarbzahl) as the aromatic hydrocarbons tolerance of the purity of purified petroleum benzin particularly, so, the tolerance of undersaturated non-aromatics impurity also is provided.According to the needs of chemical industry, the bromine index of purified petroleum benzin should be no more than the limit 20, and the pickling chromatic number should be no more than the limit 1.
In the used method of known aromatics separation, at first the mixture that contains aromatic hydrocarbons is carried out extractive distillation or liquid-liquid extraction.But in order to reach above-mentioned purity, the aromatic fraction that is produced by extraction needs the second complicated step to handle.Usually, carried out for second step and handle, wherein handle cut or with vitriol oil washing or with Fuller's earth.The post-treating method of two kinds of chemistry all is complicated and costliness.The processing of the acid sludge that is produced by sulfuric acid scrubbing is complicated and costliness.The reaction of carrying out with Fuller's earth at high temperature causes forming polymkeric substance, and it is still attached on the Fuller's earth.Simultaneously, form the oligopolymer that causes than higher pickling chromatic number by undersaturated olefinic non-aromatics.After handling with Fuller's earth, need complicated and distillation costliness to separate pure aromatics and non-aromatics.
The invention provides a kind of method of producing highly purified aromatic hydrocarbons based on above problem, this method satisfies all requirements about the purity of industrial defined, the particularly requirement of bromine index and pickling chromatic number, and this method is except the reliability of its function, and it also has simple and the low excellent characteristics of expense.The present invention is also based on a kind of device of realizing this method is provided.
Terms of settlement as this technical barrier, the invention provides a kind of method of producing highly purified aromatic hydrocarbons by reformed gasoline, wherein, in the first process steps reformed gasoline selective hydrogenation, for this reason, hydroconversion condition should be such, be that main non-aromatics, particularly alkene, diolefine and alkatrienes are by hydrogenation, thereafter, in second process steps, the product selection hydrogenation and that contain aromatic hydrocarbons in first process steps is separated into aromatic hydrocarbons and non-aromatics by extractive distillation and/or liquid-liquid extraction.
Within the scope of the invention, reformed gasoline also refers to contain the reformation cut of reformed gasoline or reformed gasoline or the mixture of distillation fraction.
Based on this understanding, promptly pass through the unsaturated non-aromatics in the reformed gasoline, particularly the extractive distillation and/or the liquid-liquid extraction of the selection hydrogenation of alkene, diolefine and alkatrienes and hydrogenation products combine, and can produce the aromatic hydrocarbons of extreme high purity and have made the present invention.Also made the present invention based on the knowledge of mentioning at this paper beginning, promptly in the above-mentioned extracting process of producing highly purified aromatic hydrocarbons, particularly make that owing to alkene the pickling chromatic number of extraction product is very high, and extremely low diene content has made the pickling chromatic number very high.Specifically, determine, especially C
6-cyclic diolefine, C
6-diene and C
6-triolefin causes high pickling chromatic number.This is specially adapted to above-mentioned those alkene, and the boiling point of those alkene approaches the boiling point of benzene, so it is difficult to separate with benzene.According to the present invention, particularly these alkene were selected hydrogenation at hydrogenation step before extraction step.According to the present invention, owing to select hydrogenation and extractive distillation thereafter and/or liquid-liquid extraction to combine, so obtain that bromine index is lower than 20, the pickling chromatic number is lower than 1 aromatic hydrocarbons.At this on the one hand, the pure aromatics of producing by method of the present invention has satisfied chemical industry all requirements about bromine index and pickling chromatic number.Simultaneously, this method is uncomplicated not expensive yet.Therefore, compare with known method, this method has considerable advantage.
The method according to this invention is highly significant embodiment preferred within the scope of the present invention, mainly contain benzene as the reformation cut of aromatic hydrocarbons part as reformed gasoline.In order to produce this reformation cut or distillation fraction, reformed gasoline was carried out fractionation before the selection hydrogenation, so that obtain only containing basically the reformation cut of benzene as aromatic hydrocarbons.This embodiment of the method according to this invention is characterized in that having following advantage: make reformed gasoline take off benzene on the one hand, can obtain purified petroleum benzin simultaneously on the other hand, it has significant importance for chemical industry.On grounds of health, the benzene that takes off that further be processed into the reformed gasoline of vehicle fuel is very important, and the content of the benzene in the reduction motor spirit has become a more and more important problem.According to another embodiment preferred of the present invention, the carbon index that contains selection is C
XAromatic hydrocarbons or the carbon index that contains several selections be C
X, C
YThe reformation cut of aromatic hydrocarbons as reformed gasoline.Produce such reformation cut or distillation fraction by reformed gasoline by fractionation, wherein other carbon exponential aromatic hydrocarbons is separated by distillation basically.According to embodiment preferred, the reformation cut only contains for example C of a carbon exponential aromatic hydrocarbons
6Or C
8Aromatic hydrocarbons.According to another embodiment preferred of method of the present invention, the reformation cut contains two or three its boiling points of carbon index preferably near the aromatic hydrocarbons of the boiling point of benzene, toluene or dimethylbenzene.Embodiment according to the method described in claim 2 and 3 of the present invention has following advantage: can obtain relating to pure especially aromatic hydrocarbons aspect bromine index and the pickling chromatic number.Such embodiment according to method of the present invention proves successful especially, wherein, in first process steps, is supported on nickel on the carrier or the palladium hydrogenation catalyst as hydrogenation.The nickel or the palladium that preferably are supported on the alumina supporter are used as hydrogenation catalyst.But the hydrogenation catalyst of other composition also can be used within the scope of the invention.Adjust the hydroconversion condition of selecting hydrogenation according to desired hydrogenation reaction and desired hydrogenation conversion.Those skilled in the art can adjust these conditions, and for example the pressure in the hydrogenator, temperature, catalyzer are formed, hydrogen/hydrocarbon than and productivity and column volume.Preferably select hydrogenation to carry out by this way, i.e. the particularly complete hydrogenation of diolefine and alkatrienes.According to embodiment preferred of the present invention, adjust hydroconversion condition in such a way: i.e. the complete hydrogenation of conjugated diolefine and alkatrienes.Preferably boiling point approaches the boiling point of benzene and therefore is difficult to and the isolating C of benzene
6-diene and C
6-triolefin and C
6-alkatrienes comes hydrogenation as far as possible fully by selecting hydrogenation.
After the hydrogenation, remove gaseous fraction from hydrogenator, the liquid aromatic hydrocarbons of selecting hydrogenation leads to extractive distillation and/or liquid-liquid extractor with the gas of dissolved remnants still.For extractive distillation and liquid-liquid extraction, use the solvent of selecting as extraction agent usually, want isolating material so that from remaining material, separate.In the scope of method of the present invention, aromatic hydrocarbons is dissolved in the used selective solvent, forms extraction liquid with this solvent, removes non-aromatics by raffinate simultaneously.Embodiment according to method of the present invention, verified wherein extractive distillation and/or liquid-liquid extraction are successful especially with the solvent of following selection, and these solvents are the derivative of N-N-formyl morpholine N-, N-Methyl pyrrolidone, tetramethylene sulfone, ethylene glycol or ethylene glycol.According to embodiment preferred of the present invention, the morpholine that replaces with the N-that 1-8 carbon atom arranged on the substituting group is as selective solvent.According to another embodiment preferred of method of the present invention, the alkane glycol of 2-5 carbon atom and/or their list and/or dialkyl ether are arranged as selective solvent.Within the scope of the invention, the mixture of said solvent also can be used as selective solvent.In addition, also can use other solvent of the selective solvent that is suitable as separating and extracting component aromatic hydrocarbons.Also can use solvent/water mixture.
Within the scope of the invention, can use the mixture of the distillation fraction of the mixture of the crude product that contains aromatic hydrocarbons of the reformed gasoline of selecting hydrogenation and other hydrogenation and/or these crude products in second process steps that extracts therein.
After extractive distillation and/or the liquid-liquid extraction, very advantageously from selective solvent, separate pure aromatics by distillation.
Below, only the present invention will be described in more detail according to the accompanying drawing that embodiment is described.For this purpose, Fig. 1 represents to implement the device of method of the present invention, and Fig. 2 represents following embodiment that is described in detail 1 and 2 graphic representation.
Below, according to the device of enforcement method of the present invention shown in Figure 1 method of the present invention is illustrated.Fig. 1 represents to implement the device of method of the present invention, comprises hydrogenator 1 and extraction plant thereafter 2.Hydrogenation unit 1 has first feeding line 3 that reformed gasoline is provided.In this embodiment, the reformation cut of the fractionation of reformed gasoline distillation generation enters hydrogenator 1 by pipeline 3.Hydrogenator 1 has second feeding line 4 that hydrogen is provided.Within the scope of the invention, the hydrogen-rich gas that provides also is provided the hydrogen that is provided.Hydrogenator 1 also has a fixed bed of being made up of hydrogenation catalyst.In an embodiment, nickel or the palladium that preferably is loaded on the alumina supporter is used as catalyzer.Adjust the hydroconversion condition of selecting hydrogenation according to needed hydrogenation reaction and needed hydrogenation conversion, for example the temperature in the hydrogenator 1, pressure, hydrogen/hydrocarbon ratio and productivity and column volume.Gaseous fraction is left hydrogenator 1 by vent line 10.Select the product liquid selection hydrogenation and that contain aromatic hydrocarbons that hydrogenation obtains to leave reactor 1 with the gas of dissolved remnants still by connection line 5.
According to embodiment preferred of the present invention, and in the embodiment according to Fig. 1, the water distilling apparatus 9 of fractionation by distillation selective solvent and pure aromatics is attached to first vent line 7.In embodiment, get back to extraction distillation column by the selective solvent that distillation removes by feeding unit 6 at water distilling apparatus 9 according to Fig. 1.Further utilize by 11 discharges of pure aromatics pipeline or continuation at the pure aromatics of water distilling apparatus 9 by fractionation by distillation.
Below, reference example further specifies the present invention.In this embodiment, listed the bromine index of ASTM D-1492, the pickling chromatic number of ASTM D-848 (Acid Wash Color, AWC) and the muddy chromatic number of ASTM D-1209.
At first, according to prior art or with reference to above-mentioned known method, the rich benzene reformation cut that is obtained by catforming process is carried out extractive distillation.The product that is used for extractive distillation shows that this content increases (seeing Table 1) with the increase of the catalyst operation time of reforming catalyst than higher olefin(e) centent.After the extractive distillation, the non-aromatics content＜1000ppm of benzene product, bromine index＜20, the pickling chromatic number always surpasses 1.Confirm that the high pickling chromatic number of benzene product is because the alkene, particularly C of trace
6-cyclic diolefine (particularly methyl isophthalic acid, 3-cyclopentadiene, bp:73 ℃ and 1, bp:81.5 ℃) or C
6-diene and C
6-triolefin (methyl isophthalic acid particularly, the 3-pentadiene, bp :～76 ℃ or 1,3, the 5-hexatriene, bp :～76.6 ℃ or 2,6-hexadiene, bp:80 ℃) cause.Because the boiling point of these alkene is near the boiling point of benzene, they are difficult to separate with benzene.Find that even Wei Liang methyl isophthalic acid especially, 3-cyclopentadiene (MCPDEN) also causes the high pickling chromatic number of benzene product.As an example, the MCPDEN of 5ppm is added in the purified petroleum benzin of pickling chromatic number＜1, thus, the pickling chromatic number is increased to 2.Following table 1 expression is relevant with the catalyzer operating time of reforming catalyst with MCPDEN content about the benzene of extractive distillation.The weight ratio of the selective solvent/hydrocarbon of extractive distillation is 2.4.After this, the product that provides as extractive distillation is provided the product that uses, and the benzene product refers to the product after the extractive distillation.
MCPDEN ppm 35 83 900 the MCPDEN ppm 15 25 139 in benzene product of the benzene % weight 60 58 61 of table 1 catalyzer operating time hours 100 1,000 1500 in the product that uses in the product that uses
Table 1 expression, the benzene product still contains the MCPDEN of high level after the extractive distillation, and this leads
Cause high pickling chromatic number.Between the temperature of 160 ℃ and 200 ℃, clean the benzene product then with Fuller's earth.The bromine index that the product that this Fuller's earth is handled shows is 120, pickling chromatic number＞14, Hazen color index are 380.MCPDEN and other C
6-diene is transformed fully.Next step need distill by Fuller's earth handles the product that obtains.The bromine index that the purified petroleum benzin that obtains of distillation shows is 4, pickling chromatic number＜1, Hazen color index＜3.But this treatment process of mentioning at last is very complicated and expensive.
Among four embodiment below,, before extractive distillation, select hydrogenation, to hydrogenation of olefins, and prevent that as far as possible aromatic hydrocarbons is converted into stable hydrocarbon with optionally according to the described method of the present invention of claim 1.
Embodiment 1 (table 2)
For this embodiment, use the reformation cut that maximum benzene content is arranged of catforming process production, it contains, and 65ppm toluene, bromine index are 3000, MCPDEN content 120ppm.In table 2, listed test conditions and the measuring result of embodiment 1a, selection hydrogenation wherein of no use and only use extractive distillation.In embodiment 1b-1d, select hydrogenation and extractive distillation to be used in combination according to method of the present invention.As the catalyzer of selecting hydrogenation, three all embodiment carry the aluminum oxide of nickel as catalyzer.In embodiment 1b-1d, select hydrogenation with a kind of like this method, promptly always only there is 0.96% used benzene to be hydrogenated into and is hexanaphthene.In all embodiment 1a-1d, as solvent, it is 50 that the theory of ED tower is separated progression with the N-N-formyl morpholine N-in extractive distillation (ED).The solvent under the condition of extractive distillation/KW-amount ratio of listing in table refers to the weight ratio of the hydrocarbon of selective solvent and use in solvent tower.Distillation tower need heat to refer to be connected in after the solvent tower the heat that needs with water distilling apparatus that separates purified petroleum benzin from selective solvent or distillation tower 9.This table and below table 3 and 4 in the heat that needs represent with the benzene that kJ/kg produces.
It is extractive distillation (ED) condition that table 2 embodiment 1a 1b 1c 1d selects hydrogenation no: products benzene content % weight 66.5 66.1 66.1 66.1 toluene level ppm 65 65 65 65MCPDEN content ppm 120＜1＜1＜1 bromine index mg Br that needs heat kJ/kg 996 984 988 963ED to use that needs heat kJ/kg 712 833 708 649 destilling towers of solvent/KW amount ratio kg/kg 2.3 2.7 2.3 2.0ED towers2The benzene product of/100g 3,000 330 330 330ED: benzene content % weight---each all＞99.96---toluene level ppm 140 130 125 112MCPDEN content ppm 41＜1＜1＜1 bromine index mg Br
2/ 100g 32 136 pickling chromatic numbers 7＜1＜1＜1 muddy chromatic number＜3＜3＜3＜3
Value representation in table 2, for selecting hydrogenation, the bromine index of reformation cut drops to 330.In addition, select hydrogenation to reduce C
6-diene content is to the following concentration of its detectability.As an example, this tabular has gone out MCPDEN content, and it is reduced to＜1ppm.Value for the benzene product of extractive distillation shows, in embodiment 1a, do not select hydrogenation, measure disadvantageous high bromine index and disadvantageous high pickling chromatic number, select hydrogenation and in embodiment 1b-1d, use, bromine index rests on＜and 10, pickling chromatic number＜1 is so the purified petroleum benzin of production has satisfied all requirements.Embodiment 1b-1d comparison shows that, even uses than being 2.0 o'clock at solvent/hydrocarbon (KW), still can produce the purified petroleum benzin that satisfies these required values.Using this lower ratio to mean in extractive distillation and distillation tower has higher productivity and lower unit to need heat with same Sopwith staff is very little.
Embodiment 2 (table 3)
For this embodiment, use the reformation cut that is equivalent to embodiment 1.For select hydrogenation use aluminum oxide as the palladium of carrier as catalyzer.In this example, select hydrogenation to relax than embodiment 1, to such an extent as to being hydrogenated into, only about 0.29% benzene is hexanaphthene.The bromine index of the product of the employed hydrogenation of extractive distillation is 1,730, and MCPDEN content is 4ppm.In all embodiment 2a-2d, extractive distillation all uses the N-N-formyl morpholine N-as selective solvent, and it is 50 that the theory of solvent tower is separated progression.
Table 3: it is extractive distillation (ED) condition that embodiment 2a 2b 2c 2d selects hydrogenation no: the products benzene content % weight 70.3 70.1 70.1 70.1 toluene level ppm 101 93 93 93MCPDEN content ppm 135 444 bromine index mg Br that need heat kJ/kg 1,177 1,181 1168 1093ED to use that need heat kJ/kg 735 729 657 544 destilling towers of solvent/KW amount ratio kg/kg 2.7 2.7 2.4 2.0ED towers2The benzene product of/100g 3,260 1,730 1730 1730ED: benzene content % weight＞99.96＞99.96＞99.96＞99.96 toluene level ppm, 98 103 98 110MCPDEN content ppm, 56 232 bromine index mg Br
2The muddy chromatic number in/100g 43 8 18 56 pickling chromatic number 6＜1＜12＜3＜3＜3＜3
Numerical value in table 3 shows, compares with embodiment 1, and embodiment 2b-2d promptly reaches lower solvent/hydrocarbon (KW) than mitigation owing to the hydrogenation degree of depth is low and uses than 2.0, so do not obtain the bromine index and the pickling chromatic number value of satisfaction.But, embodiment 1 and 2 relatively, particularly about comparison shows that of embodiment 1b-2b, by adjusting hydroconversion condition or solvent/hydrocarbon (KW) usage ratio, this process can optimizing to conditions needed.
In Fig. 2, the bromine index of purified petroleum benzin is expressed as the function that the solvent/hydrocarbon of extractive distillation (KW) uses ratio.Measurement point 1a represents the corresponding value that obtained by the embodiment 1a in the table 2, its selection hydrogenation of no use.The corresponding value that embodiment 1b-1d in the successive curve representation table 2 obtains, selection hydrogenation wherein is to carry out in such a way, promptly about 0.96% used benzene is hydrogenated into and is hexanaphthene.Measurement point 2a represents not select the corresponding embodiment in the table 3 of hydrogenation.The point dashed curve is represented the embodiment 2b-2d in the table 3, and selection hydrogenation wherein is to carry out in such a way, and promptly about only 0.29% used benzene is hydrogenated into and is hexanaphthene.Dotted line among Fig. 2 is represented the ultimate value 20 of bromine index.Fig. 2 represents, according to needed result, promptly on the one hand according to the loss of acceptable benzene, on the other hand according to needed bromine index, uses ratio by changing the hydroconversion condition or the hydrogenation degree of depth and changing solvent/hydrocarbon (KW), can change this method.
Embodiment 3 (table 4):
In the scope of this embodiment, the benzene that takes off that is used to produce the reformed gasoline of purified petroleum benzin carries out in accordance with the method for claim 2.Is final boiling point that 165 ℃ reformed gasoline at first carries out the fractionation distillation.The distillatory overhead product contains 98% used benzene.Table 4 expression, the embodiment 3a of selection hydrogenation of no use and select the embodiment 3b and the 3c of hydrogenation with the catalyzer that aluminum oxide supports nickel.Select hydrogenation to carry out in such a way, i.e. the loss of benzene approximately is 0.89%.In extractive distillation, in three all embodiment 3a-3c, all use the N-N-formyl morpholine N-, and the theory of solvent tower separation progression is 48 as selective solvent.
Table 4: it is the condition of extractive distillation (ED) that embodiment 3a 3b 3c selects hydrogenation no: products benzene content % weight 17.3 17.1 17.1 toluene level ppm 350 304 304MCPDEN content ppm 44＜1＜1 bromine index mg Br that needs heat kJ/kg 1,473 1498 926ED to use that needs heat kJ/kg 4,985 5,006 3089 destilling towers of solvent/KW amount ratio kg/kg 2.3 2.3 1.5ED towers2The benzene product of/100g 5,060 650 650ED: benzene content % weight＞99.7＞99.7＞99.7 toluene level % weight, 0.195 0.183 0.176MCPDEN content ppm, 20＜1＜1 bromine index mg Br
2/ 100g 25＜5＜16 pickling chromatic numbers 5＜1＜1 muddy chromatic number＜3＜3＜3
Embodiment 3a shows, does not select hydrogenation, does not still reach satisfied bromine index and pickling chromatic number value in the benzene product.Embodiment 3b and 3c comparison shows that, under the condition (benzene loss 0.89%) of the hydrogenation of selecting, use than being 1.52 o'clock at solvent/hydrocarbon (KW), still can obtain satisfied bromine index and pickling chromatic number value.At this on the one hand, present embodiment is the optimization embodiment with reference to the method for the present invention of above-mentioned Fig. 2.In embodiment 3c, use with extremely low solvent/hydrocarbon (KW) than and therefore on the one hand less energy-consumption also obtain the satisfactory result of bromine index and pickling chromatic number value on the one hand under the fewer situation of the loss of benzene.Embodiment 4 (table 5):
For this embodiment, use the reformation cut that contains aromatic hydrocarbons benzene, toluene, ethylbenzene and dimethylbenzene, liquid-liquid extraction carries out with this reformation cut.As selective solvent, among three all embodiment 4a-4c, all use the mixture of N-N-formyl morpholine N-/water (95/5), and the theory of liquid-liquid extraction tower separation progression is 50.As the selection hydrogenation catalyst of embodiment 4b and 4c, use the nickel be supported on the aluminum oxide, select hydrogenation to carry out in such a way, promptly the loss that becomes the benzene of hexanaphthene by hydrogenation is 1%.Specific fuel consumption in the table 5 is defined as the kJ/kg aromatic product.
Table 5: it is the condition of liquid-liquid extraction (FFE) that embodiment 4a 4b 4c selects hydrogenation no: products benzene content % weight 7.0 7.0 7.0 toluene level % weight 19.3 19.2 19.2 ethylbenzene that BTX uses among specific fuel consumption kJ/kg 1,873 1690 1868FFE of solvent/KW amount ratio kg/kg 3.0 3.0 3.0ED towers/xylene content % weight 20.5 20.4 20.4MCPDEN content ppm 38＜1＜1 bromine index mg Br2The benzene product benzene content % weight of/100g 5,280 510 510FFE＞99.96＞99.96＞99.96 toluene level ppm, 145 152 143 ethylbenzene/xylene content ppm---MCPDEN content ppm 125＜1＜1 bromine index mg Br2The muddy chromatic number in/100g 47 62 pickling chromatic number＞14＜1＜1＜3＜3＜3
As a part of liquid-liquid extraction, with selective solvent aromatics separation benzene, toluene, ethylbenzene and dimethylbenzene.From the aromatic product that extraction is produced, distill purified petroleum benzin.Embodiment 4a shows, bromine index and the pickling chromatic number value of not selecting hydrogenation, purified petroleum benzin not to meet the requirements.But obtain optimal results with above-mentioned additional selection hydrogenation.
Claims (12)
1. method of producing pure aromatics by reformed gasoline, wherein, in the first process steps reformed gasoline selective hydrogenation, hydroconversion condition is such, be that main non-aromatics, particularly alkene, diolefine and alkatrienes are by hydrogenation, thereafter, in second process steps, product the selecting property hydrogenation that obtains in first process steps and that contain aromatic hydrocarbons is separated into aromatic hydrocarbons and non-aromatics by extractive distillation and/or liquid-liquid extraction.
2. according to the process of claim 1 wherein the reformation cut as reformed gasoline, it mainly contains benzene as the aromatic hydrocarbons composition.
3. according to the process of claim 1 wherein that the carbon index that contains selection is C
XAromatic hydrocarbons or the carbon index that contains several selections be C
X, C
YThe reformation cut of aromatic hydrocarbons as reformed gasoline.
4. according to the method for one of claim 1-3, wherein carry out hydrogenation with the nickel or the palladium that are supported on the carrier as hydrogenation catalyst in first process steps.
5. according to the method for one of claim 1-4, wherein hydroconversion condition is such, and promptly conjugated diene and alkatrienes are by complete hydrogenation.
6. according to the method for one of claim 1-5, wherein extractive distillation and/or liquid-liquid extraction carry out with following selective solvent, and these solvents are the derivative of N-N-formyl morpholine N-, N-Methyl pyrrolidone, tetramethylene sulfone, ethylene glycol or ethylene glycol.
7. according to the method for one of claim 1-6, the morpholine that wherein using has 1-8 carbon atom on substituting group N-replaces is as selective solvent.
8. according to the method for one of claim 1-7, wherein use alkane glycol that 2-5 carbon atom arranged and/or its list and/or dialkyl ether as selective solvent.
9. according to the method for one of claim 1-8, wherein after extractive distillation and/or the liquid-liquid extraction, from selective solvent, separate pure aromatics by distillation.
10. a device of implementing the method for one of claim 1-9 comprises
Hydrogenator (1) and extraction plant thereafter (2),
Wherein hydrogenator (1) comprises second feeding line (4) that first feeding line of reformed gasoline (3) is provided and hydrogen is provided, wherein extraction plant (2) is connected on the hydrogenator (1) by connection line (5), the product that pipeline (5) is used to select the liquid of the selection hydrogenation that hydrogenation comes out to contain aromatic hydrocarbons enters this extraction plant (2), and wherein extraction plant (2) is equipped with the feeding unit (6) of selective solvent and discharges selective solvent and first vent line (7) of the extraction liquid that aromatic hydrocarbons is formed and discharge contain second vent line (8) of the raffinate of non-aromatics.
11. according to the device of claim 10, wherein extraction plant (2) is an extraction distillation column.
12. according to the device of claim 10 or 11, wherein the device of fractionation by distillation selective solvent and pure aromatics (9) is connected to first vent line (7) that is used for extraction liquid.
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| CN101724456A (en) * | 2008-10-23 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation method for producing aromatics extraction raw material |
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| CN1068033C (en) * | 1998-10-13 | 2001-07-04 | 中国石油化工集团公司 | Saturated hydrogenation of olefin of reforming oil |
| CN1081222C (en) * | 1999-06-23 | 2002-03-20 | 中国石油化工集团公司 | Catalytic conversion process for reducing content of olefin in liquefied gas and gasoline |
| WO2005003261A1 (en) * | 2003-07-04 | 2005-01-13 | Beijing Grand Golden-Bright Engineering & Technologies Co., Ltd. | A method for recombining catalytic hydrocarbons |
| EA008121B1 (en) * | 2003-07-04 | 2007-04-27 | Бейджин Гранд Голден-Брайт Инджиниринг Энд Текнолоджиз Ко., Лтд. | Method for processing catalysate |
| CN101091835B (en) * | 2006-06-22 | 2010-05-12 | 中国石油化工股份有限公司 | Extractive distillation method with heat exchange through parallel connection |
| CN101423451B (en) * | 2007-10-31 | 2013-01-09 | 中国石油化工股份有限公司 | Catalytic conversion method for preparing light olefins and aromatic hydrocarbons from biological oil |
| CN101724456A (en) * | 2008-10-23 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrogenation method for producing aromatics extraction raw material |
| CN101724456B (en) * | 2008-10-23 | 2013-12-25 | 中国石油化工股份有限公司 | Hydrogenation method for producing aromatics extraction raw material |
| CN103805273A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Method for olefin removal of reformate |
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