CN1143841C - Process for preparing high-purity butylene-1 from sulfur-contained c4 fraction - Google Patents
Process for preparing high-purity butylene-1 from sulfur-contained c4 fraction Download PDFInfo
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- CN1143841C CN1143841C CNB001293532A CN00129353A CN1143841C CN 1143841 C CN1143841 C CN 1143841C CN B001293532 A CNB001293532 A CN B001293532A CN 00129353 A CN00129353 A CN 00129353A CN 1143841 C CN1143841 C CN 1143841C
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Abstract
The present invention relates to a method for producing high-purity butylene-1 with mixed C4 containing sulfur of byproducts of catalytic cracking. The method has the goal that the separation of butylene-1 from mixed C4 fractions and the elimination of compounds containing sulphur in C4 through distillation are carried out simultaneously, namely that most of isobutylene is eliminated through etherification reaction, butylene-1 is separated from light C4 components and heavy C4 components through fractionation, the content of sulfide in products of butylene-1 is lower than the content of sulfide in raw materials simultaneously, and at least partial butadiene is selectively hydrogenized into monoolefin through selective hydrogenation reaction. At least partial butylene-2 is isomerized into butylene-1 through isomerization reaction if necessary.
Description
The present invention relates to produce the method for high-purity butylene-1, particularly utilize the method for the sulfur-bearing mixed c 4 production high-purity butylene-1 of catalytic cracking by-product with mixed c 4.
High-purity butylene-1 mainly as the comonomer of ethene, is produced high density polyethylene(HDPE), linear low density polyethylene etc.Just because of be as polymerization single polymerization monomer, very high to its purity requirement, as butene-1 content greater than 99% (m/m), butadiene content＜120ppm, sulphur content＜1ppm etc.
The economic raw material sources of producing butene-1 are mixed c 4s of cracking petroleum hydrocarbon vapor or catalytic cracking by-product.
Mainly comprise Trimethylmethane, butene-1, iso-butylene, maleic-2, anti-butene-2, normal butane and few butadiene etc. in the raffinate carbon four behind the mixed c 4 process extraction recovery divinyl of cracking petroleum hydrocarbon vapor by-product, impurity wherein (particularly sulphur) seldom.The iso-butylene very approaching with the butene-1 boiling point can generate methyl tertiary butyl ether (MTBE) with the methyl alcohol selective reaction.Thereby the realization butene-1 separates with iso-butylene, and residue carbon four was produced the technology of high-purity butylene-1 through selecting hydrogenation and fractionation by distillation after CN1116126A disclosed and utilized etherificate.
The mixed c 4 of catalytic cracking by-product is except containing Trimethylmethane, butene-1, iso-butylene, maleic-2, anti-butene-2, beyond carbon such as normal butane and few butadiene four components, also contain mercaptan, thioether, Methyl disulfide, methylethyl two sulphur, sulfocompounds such as diethyl two sulphur, and after these sulfocompounds are adsorbed onto on the catalyzer, can reduce the selection of catalysts hydrogenation activity, guarantee in the product butadiene content requirement that touches the mark, just must reduce the treatment capacity of unit time unit's catalyzer, improve the mol ratio of temperature of reaction or raising hydrogen and divinyl, the isomerization rate that these measures all will cause the butene-1 isomery to turn to butene-2 increases, and reduces the productive rate of butene-1.In order to make in the product sulphur content less than 1ppm, and reduce selecting the influence of hydrogenation catalyst, prior art is to utilize technologies such as oxidation style, extraction process to remove wherein sulfocompound, this complex technical process and energy consumption height earlier.
The purpose of this invention is to provide the processing method of mixed c 4 logistics direct production high-purity butylene-1 that a kind of usefulness contains the catalytic cracking by-product of sulphur compound, promptly from the hybrid C 4 cut fractionation by distillation butene-1 time, distillation removes the sulfocompound among the C4.
The mixed c 4 logistics elder generation that overall embodiment of the present invention is the catalytic cracking by-product removes after most of iso-butylene by etherification reaction, hydration reaction or isobutylene dimerization, utilize fractionation that butene-1 is separated with light, heavy carbon four components, make sulfide content in the butene-1 product be lower than sulfide content in the raw material simultaneously, and utilize selective hydrogenation reaction to make to the selected monoolefine that is hydrogenated to of small part divinyl, can also make to the small part butene-2 by isomerization reaction in case of necessity to be turned to butene-1 by isomery.Perhaps hydrogenation selected in the mixed c 4 logistics of catalytic cracking by-product successively, removed iso-butylene, reaction process such as fractionation, isomerization, wherein be used to remove the reaction of most of iso-butylene, preferred etherification reaction.
Below in conjunction with accompanying drawing the present invention is further specified (not indicating enforcement well known to those skilled in the art pump essential to the invention, valve, interchanger etc. among the figure):
As shown in Figure 1, make iso-butylene and the methyl alcohol selective reaction generation methyl tertiary butyl ether (MTBE) very approaching through etherificate with the butene-1 boiling point, thereby contain Trimethylmethane at least after most of iso-butylene removed by conversion, butene-1, maleic-2, anti-butene-2, normal butane and few butadiene, iso-butylene, the C3 cut, the catalytic cracking hybrid C 4 logistics 1 of sulfocompound feeds first distillation tower (common distillation tower) 2, and the logistics 3 that obtains from cat head comprises than the low-boiling Trimethylmethane of butene-1, the C3 cut, the part sulfocompound, the by product dme of etherification procedure and the water that can form azeotrope with hydro carbons, methyl alcohol etc.; From the logistics 4 that the tower still obtains, comprise butene-1, butene-2 (comprising maleic-2, anti-butene-2, down together), normal butane, a small amount of MTBE and remaining sulfocompound.
The operational condition of distillation tower 2 is: pressure 0.3～2.0MPa, 30～90 ℃ of tower top temperatures, reflux ratio 5～200.
Logistics 4 enters second distillation tower (catalytic distillation tower) 5, this tower comprises 4 parts at least, that be positioned at topmost is the conventional distillation district 5A of filling conventional filler or column plate, that be positioned at the 5A bottom is the reactive distillation zone 5B that hydrogenation catalyst is selected in filling, near the feed entrance point is the common distillation zone 5C of filling conventional filler or column plate, what be positioned at the 5C bottom is that filling can make the butene-2 isomery turn to the reactive distillation zone 5D of the catalyzer of butene-1, can load conventional filler or column plate as required in reactive distillation zone 5D bottom.Reacting the needed logistics 8 that contains hydrogen enters in the tower from the optional position of reactive distillation zone 5D bottom.Can obtain needed product stream 6 (when containing components such as methane, ethane, ethene, propane, propylene the hydrogen from cat head, hydrogen as reforming process institute by-product, can extract high-purity butylene-1 out from the side line of tower 5 rectifying sections, separate light C1～C3 cut from cat head), obtain containing the logistics 7 of trace impurity heavier normal butane, residue butene-2 and the raw material from the tower still than butene-1 boiling point.
The number of theoretical plate in 5A district is at least more than 20, obtains the high-purity butylene-1 that touches the mark and require from cat head with assurance; The number of theoretical plate in 5C district is at least more than 5; The operational condition of catalytic distillation tower 5 is: pressure 0.3～1.0MPa, and 30～80 ℃ of tower top temperatures, reflux ratio 5～100, the mol ratio of hydrogen and divinyl are 1～10, preferred 1.5～6.
If in producing to the productive rate of butene-1 when less demanding, then in second distillation tower of above-mentioned flow process, can not contain the isomerization catalyst bed floor (being the 5D district) that makes the butene-2 isomery turn to butene-1, at this moment the operational condition of catalytic distillation tower 5 (second column) is: pressure 0.3～1.0MPa, 30～80 ℃ of tower top temperatures, reflux ratio 5～100, the mol ratio of hydrogen and divinyl is 1～10, preferred 1.5～6.
In reactor 20, be monoolefine (butene-1 or butene-2) with selective hydrogenation of butadiene, the part butene-1 is turned to suitable, anti-butene-2 by isomery simultaneously.Its preferred operational condition is 30～90 ℃ of temperature of reaction, pressure 0.5～2.0MPa, and the carbon limbs amass air speed 1～40h
-1, the mol ratio of hydrogen and divinyl is 1～10mol/mol.Hydrogen can mix before advancing reactor with C-4-fraction, also can establish the hydrogen sparger in reactor; Hydrogen and C-4-fraction can and flow from bottom to top, also can be from top to bottom.
Select the reaction product 21 of hydrogenation to enter second distillation tower (catalytic distillation tower) 15, the catalyzer that can make the butene-2 isomery turn to butene-1 is housed in the appropriate location of this tower stripping section, catalyzer can be divided into a plurality of beds, can establish filler or column plate between the bed; Logistics 21 enters tower 15 backs under centrifugation, must reach the butene-1 (logistics 16) that satisfies index request from the side line of cat head or rectifying section, heavy constituent such as butene-2, normal butane are then moved to the tower still, during through the isomerization catalyst in the stripping section, turned to butene-1 by isomery to the small part butene-2, the logistics 18 of hydrogen enters in the tower from the beds bottom, so that isomerization is carried out facing under the hydrogen state, the mol ratio of hydrogen and butene-2 is 0.01～2mol/mol; The butene-1 that is generated moves to the top of tower, obtains containing the logistics 17 of components such as normal butane, heavier sulfocompound, residue butene-2 from the tower still.The operational condition of second distillation tower is: pressure 0.3～1.0MPa, 30～80 ℃ of tower top temperatures, reflux ratio 5～100.
Accompanying drawing 3 is another flow process of the present invention.Enter the fixed-bed reactor 33 that the selection hydrogenation catalyst is housed after forming the essentially identical logistics 31 that contains Trimethylmethane, butene-1, maleic-2, anti-butene-2, normal butane and few butadiene, iso-butylene, C3 cut, sulfocompound at least and the logistics 32 that contains hydrogen mixes with logistics in the accompanying drawing 11.In reactor 33, be monoolefine with selective hydrogenation of butadiene, the part butene-1 is turned to suitable, anti-butene-2 by isomery simultaneously.Its preferred operational condition is 30～90 ℃ of temperature of reaction, pressure 0.5～2.0MPa, and the carbon limbs amass air speed 1～40h
-1, the mol ratio of hydrogen and divinyl is 1～10mol/mol.Hydrogen can mix before advancing reactor with C-4-fraction, also can establish the hydrogen sparger in reactor; Hydrogen and C-4-fraction can and flow from bottom to top, also can be from top to bottom.
The logistics 34 of coming out from selective hydrogenation reaction device 33, enter first distillation tower (common distillation tower) 35, the logistics 36 that obtains from cat head contains than the by product dme of the low-boiling Trimethylmethane of butene-1, C3 cut, part sulfocompound, etherification procedure and can form water, methyl alcohol of azeotrope etc. with hydro carbons, obtains containing the logistics 37 of butene-1, butene-2, normal butane and remaining sulfide from the tower still.Logistics 37 enters second distillation tower (catalytic distillation tower) 40, and the catalyzer that can make the butene-2 isomery turn to butene-1 is housed in the appropriate location of this tower stripping section, and catalyzer can be divided into a plurality of beds, can establish filler or column plate between the bed; Logistics 37 enters tower 40 backs under centrifugation, must reach the butene-1 logistics 39 that satisfies index request from the side line of cat head or rectifying section, butene-2, normal butane, heavier heavy constituent such as sulfocompound are then moved to the tower still, during through the isomerization catalyst in the stripping section, turned to butene-1 by isomery to the small part butene-2, the logistics 38 of hydrogen enters in the tower from the beds bottom, so that isomerization is carried out facing under the hydrogen state, the mol ratio of hydrogen and butene-2 is 0.01～2mol/mol; The butene-1 that is generated moves to the top of tower, obtains containing the logistics 41 of remaining normal butane, butene-2 and heavier components such as sulfocompound from the tower still.The operational condition of first distillation tower is: pressure 0.3～2.0MPa, 30～90 ℃ of tower top temperatures, reflux ratio 5～200.The operational condition of second distillation tower is: pressure 0.3～1.0MPa, 30～80 ℃ of tower top temperatures, reflux ratio 5～100.
Flow process shown in Fig. 1,2 or 3 can be done following improvement in addition, the butene-2 isomerization catalyst bed layer that is about in the above-mentioned flow process moves on to outside second distillation tower (catalytic distillation tower), as shown in Figure 4, (for the improvement of accompanying drawing 1, this logistics is equivalent to logistics 4 to separate the hybrid C 4 logistics 51 of Trimethylmethane among the raw material C4, lighter light constituents such as sulfocompound; For the improvement of accompanying drawing 2, this logistics is equivalent to logistics 21; For the improvement of accompanying drawing 3, this logistics is equivalent to logistics 37), enter second column 52 (for the improvement of accompanying drawing 1, contain one in this distillation tower and select the hydrogenation catalyst bed, shown in the dotted line block diagram in the tower, the logistics 59 of hydrogen enters in the tower from the beds bottom), under fractionation, be met the high-purity butylene-1 (logistics 58) of index request from cat head or cat head side line, and butene-2, normal butane, heavier cuts such as sulfocompound move to tower still direction, from a certain position of stripping section side line extractum stream 53, and after mixing, the logistics 54 that contains hydrogen enters isomerization reactor 55.In reactor 55, suitable, the anti-butene-2 isomery of near small part turns to butene-1; Its preferred operational condition is 40～90 ℃ of temperature of reaction, pressure 0.5～2.0MPa, and the carbon limbs amass air speed 1～40h
-1, the mol ratio of hydrogen and butene-2 is 0.01～2mol/mol.Hydrogen can mix before advancing reactor with C-4-fraction, also can establish the hydrogen sparger in reactor; Hydrogen and C-4-fraction can and flow from bottom to top, also can be from top to bottom.The reaction product 56 of reactor 55 still turns back in the distillation tower 52, obtains containing the logistics 57 of normal butane and remaining butene-2, heavier sulfocompound etc. from the tower still of distillation tower 52.
Can also do following improvement to flow process shown in Fig. 1,2 or 3.As shown in Figure 5, (for the improvement of accompanying drawing 1, this logistics is equivalent to logistics 4 to remove hybrid C 4 logistics 61 after Trimethylmethane, the lighter light constituents such as sulfocompound; For the improvement of accompanying drawing 2, this logistics is equivalent to logistics 21; For the improvement of accompanying drawing 3, this logistics is equivalent to logistics 37), enter second column 62 (for the improvement of accompanying drawing 1, contain one in this distillation tower and select the hydrogenation catalyst bed, shown in the dotted line block diagram in the tower, the logistics 70 of hydrogen enters in the tower from the beds bottom), under fractionation, the logistics 63 that mainly contains butene-2, normal butane etc. that obtains from the tower still is divided into two portions, wherein a part of logistics 68 dischargers, another part logistics 64 then with after the logistics 65 of hydrogen mixes enters isomerization reactor 66.In reactor 66, suitable, the anti-butene-2 isomery of near small part turns to butene-1; Its preferred operational condition is 40～90 ℃ of temperature of reaction, pressure 0.5～2.0MPa, and the carbon limbs amass air speed 1～40h
-1, the mol ratio of hydrogen and butene-2 is 0.01～2mol/mol, hydrogen can mix before advancing reactor with C-4-fraction, also can establish the hydrogen sparger in reactor; Hydrogen and C-4-fraction can and flow from bottom to top, also can be from top to bottom.The reaction product 67 of reactor 66 still turns back in the distillation tower 62.
In the improvement flow process shown in accompanying drawing 4 or the accompanying drawing 5, the operational condition of first distillation tower and selective hydrogenation reaction device, with improve before operational condition in the flow process shown in pairing accompanying drawing 1, accompanying drawing 2 and the accompanying drawing 3 identical.Select the hydrogenation catalyst bed if contain in the second column, then its preferred reaction conditions is pressure 0.3～1.0MPa, 30～80 ℃ of tower top temperatures, and reflux ratio 5～100, the mol ratio of hydrogen and divinyl are 1～10.If do not select the hydrogenation catalyst bed in the second column, then the operational condition of this tower is pressure 0.3～1.0MPa, 30～80 ℃ of tower top temperatures, reflux ratio 5～100.
The present invention also is applicable to the situation of producing high-purity butylene-1 with the catalytic cracking by-product mixed c 4 logistics that does not remove most of iso-butylene, at this moment only need flow process in accompanying drawing 1,2 or 3, perhaps the front of accompanying drawing 4 or 5 described modified version flow processs adds the unit that removes iso-butylene, after promptly removing most of iso-butylene, again by above-mentioned flow performing by etherification reaction, hydration reaction or isobutylene dimerization.The unit further that removes iso-butylene in addition is added between the selective hydrogenation reaction device 33 and distillation tower 35 of accompanying drawing 3 (or through accompanying drawing 4 or 5 improved accompanying drawings 3), and is shown in Figure 42 as frame of broken lines in the accompanying drawing 3.Remove the preferred etherificate unit, unit of iso-butylene, at this moment the logistics 34 of coming out from selective hydrogenation reaction device 33, contact on an acidic catalyst (as large hole cation exchanger resin) with the methyl alcohol in the etherificate unit, make wherein iso-butylene and methyl alcohol selective reaction generate methyl tertiary butyl ether (MTBE), CN1042664A discloses the method for the synthetic MTBE of high conversion, and it is quoted in this patent in full.Through only containing a spot of iso-butylene in the logistics 43 after the above-mentioned etherificate unit, enter first distillation tower 35 again, subsequent step is constant.In a word, the etherificate unit is as long as before first distillation tower, and the by product dme of etherification procedure and the light constituents such as water, methyl alcohol that can form azeotrope with hydro carbons just can be from the cat head discharges of first distillation tower like this, and unlikely bringing in the product butene-1.
The active ingredient of described selection hydrogenation or isomerization catalyst is VI such as palladium, nickel
B, VIII family element, selecting the preferred active ingredient of hydrogenation catalyst is palladium or nickel, the preferred active ingredient of isomerization catalyst also is palladium or nickel; The carrier of catalyzer is aluminum oxide, silicon oxide or its mixture, preferred aluminum oxide; The content of palladium metal in catalyzer is 0.1～1% (weight), and the content of metallic nickel in catalyzer is 1～60% (weight), and the specific surface area of catalyzer is 5～200cm
2/ g; Selection hydrogenation that loads in described fixed bed or isomerization catalyst can be column, spherical, trifolium shape etc., selection hydrogenation that loads in described catalytic distillation tower and/or isomerization catalyst can be column, spherical, trifolium shape, be preferably and itself have fractionation and the bifunctional filler shape of katalysis, Chinese patent CN1242410 discloses double-functional packing shape Preparation of catalysts method, is quoted in this patent.
Characteristics of the present invention are, last running light in fractionation by distillation, when making high-purity butylene-1, can remove impurity such as sulfocompound, can also increase the output of butene-1 by the isomerization of butene-2 when needing.
Below in conjunction with embodiment the present invention is done and to be described in more detail:
Embodiment 1: the mixed c 4 logistics with the catalytic cracking by-product that removed most of iso-butylene is a raw material, adopt process shown in the accompanying drawing 1 to produce butene-1, the diameter of two distillation towers is 100mm, interior dress θ shape 4*4 net ring filler, wherein first distillation tower is from the middle part charging, reflux ratio is 25, and tower top pressure is 0.7MPa, 57 ℃ of tower top temperatures; The height of second each section of distillation tower is respectively 5A district 4m, 5B district 1m, 5C district 3m, 5D district 1m, and 5D bottom 3m, feed entrance point are middle part, 5C district; The Raschig ring shape catalyzer of the 10*10mm of Chinese patent CN1242249 disclosed method preparation is pressed in 5B district, the filling of 5D district, and active ingredient is a palladium, and carrier is an aluminum oxide, and loadings is respectively 1.5 liters and 4 liters; Reflux ratio is 13, and tower top pressure is 0.6MPa, and 53 ℃ of tower top temperatures, the mol ratio of hydrogen and divinyl are 1.4mol/mol.The composition of main streams such as raw material sees Table 1.As seen resulting butene-1 logistics satisfies butene-1＞99%, divinyl＜120ppm, and the index request of sulphur＜1ppm, and also 60% butene-2 isomery turns to butene-1.
The composition of table 1 embodiment 1 each logistics
| Logistics | Flow kg/h | C3 ％ | Trimethylmethane, % | Butylene-1, % | Butylene-2, % | Normal butane, % | Iso-butylene, % | Divinyl, ppm | C5 ％ | Dme, % | Methyl alcohol ppm | Sulphur ppm |
| 1 | 50.0 | 0.03 | 43.62 | 14.98 | 25.77 | 13.50 | 0.03 | 3700 | 1.55 | 0.15 | 53 | 75 |
| 3 | 22.8 | 0.06 | 95.44 | 3.97 | 0.07 | 0.03 | / | 900 | / | 0.33 | 116 | 24 |
| 4 | 27.2 | / | 0.18 | 24.21 | 47.31 | 24.79 | 0.06 | 6000 | 2.85 | / | / | 118 |
| 6 | 14.0 | / | 0.34 | 99.43 | 0.09 | 0.03 | 0.11 | 53 | / | / | / | / |
| 7 | 13.2 | / | / | 10.04 | 36.69 | 48.74 | / | 4.52 | / | / | 193 |
Embodiment 2: the mixed c 4 logistics with the catalytic cracking by-product that removed most of iso-butylene is a raw material, adopt process shown in the accompanying drawing 2 to produce butene-1, the diameter of two distillation towers is 100mm, interior dress θ shape 4*4 net ring filler, wherein first distillation tower is from the middle part charging, reflux ratio is 25, and tower top pressure is 0.7Mpa, 57 ℃ of tower top temperatures; Second input of column position is the middle part of tower, and 4 liters of the Raschig ring shape catalyzer of the 10*10mm that Chinese patent CN1242249 disclosed method prepares press in stripping section 1/3 place district filling, and active ingredient is a palladium, and carrier is an aluminum oxide; Reflux ratio is 13, and tower top pressure is 0.6Mpa, and 53 ℃ of tower top temperatures, the mol ratio of hydrogen and butene-2 are 0.05mol/mol; Fixed-bed reactor diameter 100mm wherein loads 10 liters of the cylindrical catalysts of 3*3mm, and operational condition is pressure 1.0MPa, 60 ℃ of temperature, and the carbon limbs amass air speed 5h
-1, the mol ratio of hydrogen and diolefine is 2mol/mol.The composition of main streams such as raw material sees Table 2.As seen resulting butene-1 logistics satisfies butene-1＞99%, divinyl＜120ppm, and the index request of sulphur＜1ppm, and in second distillation tower, have 68% butene-2 isomery to turn to butene-1.
The composition of table 2 embodiment 2 each logistics
| Logistics | Flow kg/h | C3 ％ | Trimethylmethane, % | Butylene-1, % | Butylene-2, % | Normal butane, % | Iso-butylene, % | Divinyl, ppm | C5 ％ | Dme, % | Methyl alcohol | Sulphur ppm | |
| 11 | 50.0 | 0.03 | 43.62 | 14.98 | 25.77 | 13. 50 | 0.03 | 3700 | 1.55 | 0.15 | 53 | 75 | |
| 13 | 22.8 | 0.06 | 95.44 | 3.97 | 0.07 | 0.03 | / | 900 | / | 0.33 | 116 | 24 | |
| 14 | 27.2 | / | 0.18 | 24.21 | 47.31 | 24.79 | 0.06 | 6000 | 2.85 | / | / | 118 | |
| 21 | 27.2 | / | 0.18 | 15.74 | 59.04 | 24.98 | 0.06 | / | 2.85 | / | / | 118 | |
| 16 | 12.5 | / | 0.39 | 99.39 | 0.06 | 0.03 | 0.13 | 40 | / | / | / | / | |
| 17 | 14.7 | / | / | 7.42 | 41.11 | 46.20 | / | / | 5.27 | / | / | 193 |
Embodiment 3: the mixed c 4 logistics with the catalytic cracking by-product that removed most of iso-butylene is a raw material, adopt flow process shown in the accompanying drawing 3 to produce butene-1, the diameter of two distillation towers is 100mm, interior dress θ shape 4*4 net ring filler, wherein first distillation tower is from the middle part charging, reflux ratio is 25, and tower top pressure is 0.7Mpa, 57 ℃ of tower top temperatures; Second input of column position is the middle part of tower, and 4 liters of the Raschig ring shape catalyzer of the 10*10mm that Chinese patent CN1242249 disclosed method prepares press in stripping section 1/3 place district filling, and active ingredient is a palladium, and carrier is an aluminum oxide; Reflux ratio is 13, and tower top pressure is 0.6Mpa, and 53 ℃ of tower top temperatures, the mol ratio of hydrogen and butene-2 are 0.05mol/mol; Fixed-bed reactor diameter 100mm wherein loads 20 liters of the cylindrical catalysts of 3*3mm, and operational condition is pressure 1.0MPa, 60 ℃ of temperature, and the carbon limbs amass air speed 5h
-1, the mol ratio of hydrogen and diolefine is 2mol/mol.The composition of main streams such as raw material sees Table 3.As seen resulting butene-1 logistics satisfies butene-1＞99%, divinyl＜120ppm, and the index request of sulphur＜1ppm, and in second distillation tower, have 69% butene-2 isomery to turn to butene-1.
The composition of table 3 embodiment 3 each logistics
| Logistics | Flow kg/h | C3 ％ | Trimethylmethane, % | Butylene-1, % | Butylene-2, % | Normal butane, % | Iso-butylene, % | Divinyl, ppm | C5 ％ | Dme, % | Methyl alcohol ppm | Sulphur ppm |
| 31 | 50 | 0.03 | 43.62 | 14.98 | 25.77 | 13.50 | 0.03 | 3700 | 1.55 | 0.15 | 53 | 75 |
| 34 | 50 | 0.04 | 43.62 | 9.74 | 31.18 | 13.69 | 0.03 | / | 1.55 | 0.15 | 53 | 75 |
| 36 | 22.6 | 0.07 | 96.32 | 3.17 | 0.07 | 0.04 | / | / | / | 0.33 | 116 | 24 |
| 37 | 27.4 | / | 0.15 | 15.16 | 56.84 | 24.95 | 0.06 | 12 | 2.83 | / | / | 118 |
| 39 | 12.8 | / | 0.32 | 99.46 | 0.06 | 0.03 | 0.13 | 51 | / | / | / | / |
| 41 | 14.4 | / | / | 9.46 | 37.12 | 47.97 | / | / | 5.44 | / | / | 193 |
Embodiment 4: the mixed c 4 logistics with the catalytic cracking by-product that removed most of iso-butylene is a raw material, adopt with the similar process of flow process shown in the accompanying drawing 1 and produce butene-1, just in second distillation tower, has only the hydrogenation catalyst of selection bed, and do not have isomerization catalyst bed layer, the diameter of two distillation towers is 100mm, the Dixon ring filler of interior dress 4*4, wherein first distillation tower is from the middle part charging, reflux ratio is 25, and tower top pressure is 0.7Mpa, 57 ℃ of tower top temperatures; Second input of column position is the middle and lower part of tower, the logistics of hydrogen is from entering below the beds in the tower, the height of each section of catalytic distillation tower is respectively beds top 4m, opening for feed to beds 3m, stripping section 4.7m, 1.2 liters of the Raschig ring shape catalyzer of the 10*10mm that Chinese patent CN1242249 disclosed method prepares press in filling in the beds, active ingredient is a palladium, and carrier is an aluminum oxide; Reflux ratio is 13, and tower top pressure is 0.6MPa, and 53 ℃ of tower top temperatures, the mol ratio of hydrogen and divinyl are 1.5mol/mol; The composition of main streams such as raw material sees Table 4.As seen resulting butene-1 logistics satisfies butene-1＞99%, diolefine＜120ppm, the index request of sulphur＜1ppm.
The composition of table 4 embodiment 4 each logistics
| Logistics | Flow kg/h | C3 ％ | Trimethylmethane, % | Butylene-1, % | Butylene-2, % | Normal butane, % | Iso-butylene, % | Divinyl, ppm | C5 ％ | Dme, % | Methyl alcohol ppm | Sulphur ppm |
| 1 | 50.0 | 0.03 | 43.62 | 14.98 | 25.77 | 13.50 | 0.03 | 3700 | 1.55 | 0.15 | 53 | 75 |
| 3 | 22.8 | 0.06 | 95.44 | 3.97 | 0.07 | 0.03 | / | 900 | / | 0.33 | 116 | 24 |
| 4 | 27.2 | / | 0.18 | 24.21 | 47.31 | 24.79 | 0.06 | 6000 | 2.85 | / | / | 118 |
| 6 | 6.2 | / | 0.39 | 99.18 | 0.27 | 0.03 | 0.13 | 40 | / | / | / | / |
| 7 | 21.0 | / | / | 0.42 | 61.03 | 33.28 | / | / | 5.27 | / | / | 193 |
Claims (26)
1. method of producing high-purity butylene-1 from the catalytic cracking by-product mixed c 4 logistics of sloughing most of iso-butylene that contains Trimethylmethane, butene-1, maleic-2, anti-butene-2, normal butane and few butadiene, iso-butylene, C3 cut, sulfocompound component, it comprises:
(1) make described feed stream enter first distillation tower, in this tower: A. isolates most of Trimethylmethane, C3 cut and part sulfocompound light constituent the described raw material from cat head; B. the most of butene-1 from the described feed stream that the tower still obtains, butene-2, normal butane heavy constituent enter second distillation tower;
(2) in second distillation tower: A. is to the selected hydrogenation of small part divinyl; B. the major part sulfocompound that enters second tower enters tower stilling branch at least; C. obtain the butene-1 product from cat head or side line.
2. method of producing high-purity butylene-1 from the catalytic cracking by-product mixed c 4 logistics of sloughing most of iso-butylene that contains Trimethylmethane, butene-1, maleic-2, anti-butene-2, normal butane and few butadiene, iso-butylene, C3 cut, sulfocompound component, it comprises:
(1) make described feed stream enter first distillation tower, in this tower: A. isolates most of Trimethylmethane, C3 cut and part sulfocompound light constituent the described raw material from cat head; B. the most of butene-1 from the described feed stream that the tower still obtains, butene-2, normal butane heavy constituent enter second distillation tower;
(2) in second distillation tower: A. is to the selected hydrogenation of small part divinyl; B. turned to butene-1 by isomery to the small part butene-2; C. the major part sulfocompound that enters second tower enters tower stilling branch at least; D. obtain the butene-1 product from cat head or side line.
3. method of producing high-purity butylene-1 from the catalytic cracking by-product mixed c 4 logistics of sloughing most of iso-butylene that contains Trimethylmethane, butene-1, maleic-2, anti-butene-2, normal butane and few butadiene, iso-butylene, C3 cut, sulfocompound component, it comprises:
(1) make described feed stream enter first distillation tower, in this tower: A. isolates most of Trimethylmethane, C3 cut and part sulfocompound light constituent the described raw material from cat head; B. the most of butene-1 from the described feed stream that the tower still obtains, butene-2, normal butane heavy constituent enter second distillation tower;
(2) in second distillation tower: A. is to the selected hydrogenation of small part divinyl; B. the major part sulfocompound that enters second tower enters tower stilling branch at least; C. obtain the butene-1 product from cat head;
(3) extract the part logistics at least out from the stripping section side line of second distillation tower or tower still and enter isomerization reactor, make to the small part butene-2 and turned to butene-1 by isomery, the logistics of coming out from isomerization reactor turns back to second distillation tower again.
4. according to claim 1,2 or 3 described methods, wherein the operational condition of first distillation tower is pressure 0.3～2.0MPa, 30～90 ℃ of tower top temperatures, reflux ratio 5～200.
5. according to claim 1,2 or 3 described methods, wherein the operational condition of second distillation tower is pressure 0.3～1.0MPa, 30～80 ℃ of tower top temperatures, and reflux ratio 5～100, the mol ratio of hydrogen and divinyl are 1～10.
6. in accordance with the method for claim 3, wherein the operational condition of isomerization reactor is pressure 0.5～2.0MPa, 40～90 ℃ of temperature, and the carbon limbs amass air speed 1～40h
-1, the mol ratio of hydrogen and butene-2 is 0.01～2mol/mol.
7. method of producing high-purity butylene-1 from the catalytic cracking by-product mixed c 4 logistics of sloughing most of iso-butylene that contains Trimethylmethane, butene-1, maleic-2, anti-butene-2, normal butane and few butadiene, iso-butylene, C3 cut, sulfocompound component, it comprises:
(1) described feed stream is entered in first distillation tower, in this tower: A. isolates most of Trimethylmethane, C3 cut and part sulfocompound light constituent the described raw material from cat head; B. the most of butene-1 from the described feed stream that the tower still obtains, butene-2, normal butane heavy constituent enter the selective hydrogenation reaction device;
(2) in the selective hydrogenation reaction device, be removed to the small part diolefine, reaction product enters second distillation tower;
(3) in second distillation tower: A. is turned to butene-1 by isomery to the small part butene-2; B. the major part sulfocompound that enters second tower enters tower stilling branch at least; C. obtain the butene-1 product from cat head or side line.
8. method of producing high-purity butylene-1 from the catalytic cracking by-product mixed c 4 logistics of sloughing most of iso-butylene that contains Trimethylmethane, butene-1, maleic-2, anti-butene-2, normal butane and few butadiene, iso-butylene, C3 cut, sulfocompound component, it comprises:
(1) described feed stream is entered in first distillation tower, in this tower: A. isolates most of Trimethylmethane, C3 cut and part sulfocompound light constituent the described raw material from cat head; B. the most of butene-1 from the described feed stream that the tower still obtains, butene-2, normal butane heavy constituent enter the selective hydrogenation reaction device;
(2) in the selective hydrogenation reaction device, be removed to the small part diolefine, reaction product enters second distillation tower;
(3) in second distillation tower: the A. major part sulfocompound that enters second tower at least enters tower stilling branch; B. obtain the butene-1 product from cat head;
(4) extract the part logistics at least out from the stripping section side line of second distillation tower or tower still and enter isomerization reactor, make to the small part butene-2 and turned to butene-1 by isomery, the logistics of coming out from isomerization reactor turns back to second distillation tower again.
9. according to claim 7 or 8 described methods, wherein the operational condition of first distillation tower is pressure 0.3～2.0MPa, 30～90 ℃ of tower top temperatures, reflux ratio 5～200.
10. according to claim 7 or 8 described methods, wherein the operational condition of selective hydrogenation reaction device is pressure 0.5～2.0MPa, 30～90 ℃ of temperature, and the carbon limbs amass air speed 1～40h
-1, the mol ratio of hydrogen and divinyl is 1.0～10mol/mol.
11. according to claim 7 or 8 described methods, wherein the operational condition of second distillation tower is pressure 0.3～1.0MPa, 30～80 ℃ of tower top temperatures, reflux ratio 5～100.
12. in accordance with the method for claim 7, wherein the mol ratio of the hydrogen of second distillation tower and butene-2 is 0.01～2mol/mol.
13. in accordance with the method for claim 8, wherein the operational condition of isomerization reactor is pressure 0.5～2.0MPa, 40～90 ℃ of temperature, and the carbon limbs amass air speed 1～40h
-1, the mol ratio of hydrogen and butene-2 is 0.01～2mol/mol.
14. a method of producing high-purity butylene-1 from the catalytic cracking by-product mixed c 4 logistics of sloughing most of iso-butylene that contains Trimethylmethane, butene-1, maleic-2, anti-butene-2, normal butane and few butadiene, iso-butylene, C3 cut, sulfocompound component, it comprises:
(1) in the selective hydrogenation reaction device, described feed stream is carried out selective hydrogenation reaction, remove wherein to the small part divinyl, reaction product enters first distillation tower;
(2) in first distillation tower, A. separates wherein most of Trimethylmethane, C3 cut and part sulfocompound light constituent from cat head; B. the most of butene-1 from the described feed stream that the tower still obtains, butene-2, normal butane heavy constituent enter in second distillation tower;
(3) in second distillation tower: A. is turned to butene-1 by isomery to the small part butene-2; B. the major part sulfocompound that enters second tower enters tower stilling branch at least; C. obtain the butene-1 product from cat head or side line.
15. a method of producing high-purity butylene-1 from the catalytic cracking by-product mixed c 4 logistics of sloughing most of iso-butylene that contains Trimethylmethane, butene-1, maleic-2, anti-butene-2, normal butane and few butadiene, iso-butylene, C3 cut, sulfocompound component, it comprises:
(1) in the selective hydrogenation reaction device, described raw material is carried out selective hydrogenation reaction, remove wherein to the small part divinyl, reaction product enters first distillation tower;
(2) in first distillation tower, A. separates wherein most of Trimethylmethane, C3 cut and part sulfocompound light constituent from cat head; B. the most of butene-1 from the described feed stream that the tower still obtains, butene-2, normal butane heavy constituent enter in second distillation tower;
(3) in second distillation tower: the A. major part sulfocompound that enters second tower at least enters tower stilling branch; B. obtain the butene-1 product from cat head.
(4) extract the part logistics at least out from the stripping section side line of second distillation tower or tower still and enter isomerization reactor, make to the small part butene-2 and turned to butene-1 by isomery, the logistics of coming out from isomerization reactor turns back to second distillation tower again.
16. according to claim 14 or 15 described methods, wherein the operational condition of selective hydrogenation reaction device is pressure 0.5～2.0MPa, 30～90 ℃ of temperature, and the carbon limbs amass air speed 1～40h
-1, the mol ratio of hydrogen and divinyl is 1.0～10mol/mol.
17. according to claim 14 or 15 described methods, wherein the operational condition of first distillation tower is pressure 0.3～2.0MPa, 30～90 ℃ of tower top temperatures, reflux ratio 5～200.
18. according to claim 14 or 15 described methods, wherein the operational condition of second distillation tower is pressure 0.3～1.0MPa, 30～80 ℃ of tower top temperatures, reflux ratio 5～100.
19. in accordance with the method for claim 14, wherein the mol ratio of the hydrogen of second distillation tower and butene-2 is 0.01～2mol/mol.
20. in accordance with the method for claim 15, wherein the operational condition of isomerization reactor is pressure 0.5～2.0MPa, 40～90 ℃ of temperature, and the carbon limbs amass air speed 1～40h
-1, the mol ratio of hydrogen and butene-2 is 0.01～2mol/mol.
21. according to any described method in the claim 1,2,3,7,8,14,15, wherein the active ingredient of selective hydrogenation of butadiene reaction catalyst system therefor is VIB or VIII family element.
22. according to any described method in the claim 1,2,3,7,8,14,15, wherein the active ingredient of selective hydrogenation of butadiene reaction catalyst system therefor is palladium or nickel.
23. according to any described method in the claim 2,3,7,8,14,15, wherein the active ingredient of butene-2 isomerization reaction catalyst system therefor is VI
BOr VIII family element.
24. according to any described method in the claim 2,3,7,8,14,15, wherein the active ingredient of butene-2 isomerization reaction catalyst system therefor is palladium or nickel.
25. according to any described method in the claim 1,2,3,7,8,14,15, with the catalytic cracking by-product mixed c 4 logistics that contains Trimethylmethane, butene-1, maleic-2, anti-butene-2, iso-butylene, normal butane and few butadiene, C3 cut, sulfocompound component is the raw material production high-purity butylene-1, it is characterized in that the logistics of catalytic cracking by-product mixed c 4 before entering first distillation tower, remove wherein most of iso-butylene by etherification reaction, hydration reaction or isobutylene dimerization earlier.
26. in accordance with the method for claim 25, it is characterized in that the logistics of catalytic cracking by-product mixed c 4 before entering first distillation tower, remove wherein most of iso-butylene by etherification reaction earlier.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255086B (en) * | 2007-03-01 | 2010-09-15 | 中国石油化工股份有限公司 | Method for cracking C_4 and preparing olefin by refinery C_4 |
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| CN101362671B (en) * | 2008-09-12 | 2011-09-07 | 中国石油化工股份有限公司 | Method for preparing polymer grade 1-butene by high sulfur content four carbon compounds catalysis from refinery |
| CN101884923B (en) * | 2009-05-13 | 2013-01-16 | 中国石油化工股份有限公司 | Nickel-based catalyst for preparing butene-2 or butene-1 by n-butene double-bond migration |
| CN103102987B (en) * | 2011-11-10 | 2015-11-25 | 中国石油化工股份有限公司 | A kind of desulfurizing process of C-4-fraction |
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| CN104926588B (en) * | 2015-06-24 | 2016-08-24 | 长岭炼化岳阳工程设计有限公司 | The method of 2-butylene and the system of 2-butylene in separation of carbon alkatetraenes in separation of carbon alkatetraenes |
| CN106552621B (en) * | 2015-09-30 | 2019-10-22 | 中国石油化工股份有限公司 | The method that 2- butylene hydro-isomerization prepares catalyst used in 1- butylene and prepares 1- butylene |
| CN112707782B (en) * | 2019-10-25 | 2023-05-02 | 中国石油化工股份有限公司 | Method for producing 1-butene from mixed carbon four raw materials |
| CN114436740A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Method and system for producing 1-butene by using mixed C4 |
| CN115010571A (en) * | 2022-06-27 | 2022-09-06 | 长沙博能科技股份有限公司 | Method for separating isobutane and 1-butene from carbon tetrachloride after etherification |
-
2000
- 2000-11-24 CN CNB001293532A patent/CN1143841C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255086B (en) * | 2007-03-01 | 2010-09-15 | 中国石油化工股份有限公司 | Method for cracking C_4 and preparing olefin by refinery C_4 |
| CN107118072A (en) * | 2017-05-08 | 2017-09-01 | 安徽海德石油化工有限公司 | A kind of method that utilization C-4-fraction produces isomery C8 alkane |
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