CN110655435A - Solid acid alkylation reaction method and reaction device - Google Patents
Solid acid alkylation reaction method and reaction device Download PDFInfo
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- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
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Abstract
The present invention provides a solid acid alkylation process comprising contacting a reaction feed comprising an alkylatable organic compound and an alkylating agent under alkylation reaction conditions in the presence of a solid acid catalyst to form an alkylate, characterized in that the process comprises the steps of contacting an alkylation reactor outlet stream with hydrogen and separating the product, and recycling a portion of the separated hydrogen-free material back to the alkylation reactor. The method increases the activity of the catalyst and improves the quality of the alkylate oil.
Description
Technical Field
The present invention relates to an alkylation reaction apparatus and a reaction method, and more particularly, to an alkylation reaction apparatus and a reaction method in the presence of a solid acid catalyst.
Background
The alkylation reaction of isobutane and butene is an important process for producing high-octane gasoline components in the petroleum refining industry, and the alkylate serving as an ideal high-octane gasoline blending component has the characteristics of high octane number, low sensitivity, low Reid process steam pressure, no olefin or aromatic hydrocarbon and low sulfur content.
At present, the production process of the alkylate oil which is industrially applied mainly comprises the sulfuric acid method and the hydrofluoric acid method, but the safety and environmental protection pressure of alkylate oil production enterprises is increasing due to the corrosivity and toxicity of sulfuric acid and hydrofluoric acid and the harm of waste acid discharge in the process flow to the environment. For this reason, since the eighties of the last century, many larger oil companies and research institutes around the world have been working on the research and development of solid acid alkylation processes, and it is expected that environmentally friendly solid acid processes can replace liquid acid processes.
The biggest problem in the use of solid acid catalysts in alkylation reactions is their extreme susceptibility to deactivation, e.g. molecular sieve catalysts, SO4 2-Alkylation activity of oxide catalyst within hours, even minutes (C)4 ＝Olefin conversion) from 100% to very low levels and the selectivity of the reaction becomes poor, resulting in a reduction in the octane number of the alkylation product, alkylate. Therefore, regeneration of solid acid alkylation catalysts is a critical issue that needs to be addressed.
Currently, there are many hydrocarbon conversion processes that employ solid acid catalysts at low temperatures, such as alkylation, isomerization, olefin oligomerization, hydroisomerization, and the like. Some of the side reactions in these hydrocarbon conversion processes, such as molecular polymerization and hydrogen transfer reactions, result in some large molecular alkanes or alkenes coating the surface of the catalyst, unlike high temperature hydrocarbon conversion processes (reforming, catalytic cracking, etc.), which are organic materials (or coke precursors) with a carbon to hydrogen ratio (C/H) < 1, rather than the coke materials with C/H > 1 produced in high temperature processes. This provides the possibility of solvent washing away such macromolecular hydrocarbon coatings.
US5,326,923 and CN1,076,386A disclose a process for the solvent extraction of a regenerated lewis acid-supported acidic hydrocarbon conversion catalyst, which process comprises first separating the catalyst from the reaction system,then using a gas selected from SO2A solvent of phenols and aromatic ethers is contacted with the lewis acid-supported alkylation catalyst to remove reaction residues adhering to the surface of the catalyst, thereby restoring the initial performance of the catalyst.
US5,489,732 and CN1,144,141A disclose a process for the hydro-regeneration of a solid acid alkylation catalyst. The method adopts hydrogen and an alkylation catalyst Pt-KCl-AlCl containing a hydrogenation active component Pt at the temperature of 10-300 ℃ and the hydrogen partial pressure of 6.9-3790 kilopascals3/Al2O3Contact, selective hydrogenation of C on the surface of the catalyst4 +Covering of hydrocarbon molecules, the activity of the catalyst is restored.
US5,523,503 discloses a process for regenerating a solid acid alkylation catalyst with a moving bed of hydrogen-saturated hydrocarbons. The method uses hydrogen saturated isobutane and Pt-containing solid acid alkylation catalyst (Pt-KCl-AlCl)3/Al2O3) Contacting to make the macromolecular hydrocarbon molecules covered on the surface of the catalyst undergo hydrogenation saturation desorption so as to restore the activity of the catalyst.
Disclosure of Invention
The inventor finds out on the basis of a great deal of experiments that a small amount of unsaturated hydrocarbon exists in the outlet stream of the alkylation reactor besides a large amount of alkane, and the unsaturated hydrocarbon is further superposed in the reactor, occupies active sites on the surface of the catalyst and generates C9+, thereby reducing the quality of alkylate; if the outlet material of the alkylation reactor is contacted with hydrogen to remove unsaturated hydrocarbon in the reaction product and then is recycled to the inlet of the alkylation reactor, the reaction and regeneration are carried out simultaneously due to the washing action of the solvent, the service life of the catalyst can be prolonged, and the quality of the alkylate oil product is also improved.
Therefore, an object of the present invention is to provide an alkylation reaction method which can prolong the service life of a catalyst and improve the quality of an alkylate oil product, and another object of the present invention is to provide a reaction apparatus for implementing the alkylation reaction method.
In order to achieve one of the objects of the present invention, there is provided a solid acid alkylation process comprising contacting a reaction feed comprising an alkylatable organic compound and an alkylating agent under alkylation reaction conditions in the presence of a solid acid catalyst to form an alkylate, characterized in that the process comprises the steps of contacting an alkylation reactor outlet stream with hydrogen and separating the product, and recycling a portion of the separated hydrogen-free material back to the alkylation reactor.
In order to achieve the second purpose of the invention, the invention provides a solid acid alkylation reaction device, which is characterized by comprising an alkylation reactor, a hydrogenation tower and a fractionating tower, wherein the alkylation reactor is connected with the hydrogenation tower, and the hydrogenation tower is used for contacting the reaction product led from the alkylation reactor and the alkylatable organic compound with hydrogen to carry out hydrogenation treatment; the fractionating tower is used for fractionating the material led out from the tower kettle of the hydro-tower to obtain the alkylate oil.
The present invention makes alkylation reaction and catalyst regeneration simultaneously, increases the activity of the catalyst and raises the quality of the alkylate oil.
Drawings
FIG. 1 is a basic apparatus and flow diagram of one embodiment of the present invention.
Detailed Description
A solid acid alkylation process of the present invention comprising contacting a reaction feed comprising an alkylatable organic compound and an alkylating agent under alkylation reaction conditions in the presence of a solid acid catalyst to form an alkylate, characterized in that the process comprises the steps of contacting an alkylation reactor outlet stream with hydrogen and separating the product, and recycling a portion of the separated hydrogen-free material back to the alkylation reactor.
In the method, the alkylatable organic compound is C4-C6 isoparaffin, and the alkylating agent is C3-C6 single-bond olefin; preferably, the C4-C6 isoparaffin is isobutane, and the C3-C6 single-bond olefin is 1-butene or 2-butene or a mixture thereof.
In the method of the invention, the solid acid catalyst can be used for low carbon iso-catalyst disclosed in the prior artThe present invention is not particularly limited to various solid acid catalysts for the alkylation of paraffins with olefins, particularly isoparaffins with olefins. For example, the solid acid catalyst may be selected from the group consisting of zeolite molecular sieve catalysts, supported heteropolyacid catalysts, SO4 2-Oxide super acidic catalyst, supported Bronsted-Lewis conjugated solid super acidic catalyst, ion exchange resin, Lewis acid treated oxide and Lewis acid treated molecular sieve catalyst. More specifically, SO disclosed in JP01,245,853, US3,962,133, US4,116,880, GB1,432,720, GB1,389,237 can be used4 2-Oxide super acid catalyst; CF disclosed in US5,220,095, US5,731,256, US5,489,729, US5,364,976, US5,288,685, EP0,714,8713SO3H/silica catalyst; Pt-AlCl disclosed in US5,391,527, US5,739,0743-KCl/Al2O3A catalyst; lewis acids such as SbF as disclosed in US5,157,196, US5,190,904, US5,346,676, US5,221,777, US5,120,897, US5,245,101, US5,012,033, US5,157,197, CN1,062,307, WO95,126,8155、BF3、AlCl3A supported oxide catalyst; catalysts containing molecular sieves such as beta, ZSM-5, etc. disclosed in U.S. Pat. Nos. 3,549,557, 3,644,565, 3,647,916, 3,917,738, 4,384,161, etc.; all of which are incorporated herein by reference. More preferably, the solid acid catalyst employed in the present invention is a zeolite molecular sieve catalyst, most preferably X, Y or beta molecular sieve as the solid acid active component.
The method is particularly suitable for the process of producing alkylate by the alkylation of C4-C6 isoparaffin and C3-C6 single bond olefin. The alkylation reaction conditions are that the reaction temperature is 10-350 ℃, the reaction pressure is 0.5-10.0 MPa, the molar ratio of the isoparaffin to the single-bond olefin is 2-500, and the weight space velocity of the single-bond olefin as a reaction raw material is 0.05-20 hours-1(ii) a Preferably, the alkylation reaction conditions are that the reaction temperature is 30-150 ℃, the reaction pressure is 2.0-5.0 MPa, the molar ratio of the isoparaffin to the single-bond olefin is 10-100, and the weight space velocity of the single-bond olefin as the reaction raw material is 0.1-1 hour-1. The reaction raw material is subjected to alkylation reactionThe top or bottom catalyst beds of the alkylation reactor are fed in sections, or from different catalyst beds of the alkylation reactor.
In the method, the conditions of the process of contacting the material flow at the outlet of the alkylation reactor with hydrogen are that the pressure is 0.5-3 MPa and the temperature at the top of the tower is 10-100 ℃; preferably, the conditions are that the pressure is 1-3 MPa and the temperature is 50-100 ℃. The mass flow of the hydrogen is preferably 0.1-1% of the mass flow of the material flow at the outlet of the reactor from the comprehensive consideration of realizing the hydrogen effect, the cost and the normal operation.
The method comprises the steps of contacting and separating the outlet material flow of the alkylation reactor with hydrogen, and then circulating a part of the separated material without hydrogen back to the alkylation reactor, wherein the material without hydrogen which is circulated back to the alkylation reactor preferably accounts for 90-97% by weight, and the other 3-10% by weight enters a fractionating tower, alkylate oil is obtained at the bottom of the fractionating tower, and isobutane recovered at the top of the fractionating tower is circulated back to the alkylation reactor.
The invention also provides a solid acid alkylation reaction device for implementing the alkylation reaction method, which is characterized by comprising an alkylation reactor, a hydrogenation tower and a fractionating tower, wherein the alkylation reactor is connected with the hydrogenation tower, and the hydrogenation tower is used for contacting reaction products and alkylatable organic compounds which are led from the alkylation reactor with hydrogen to carry out hydrogenation treatment; the fractionating tower is used for fractionating the material led out from the tower kettle of the hydro-tower to obtain the alkylate oil.
In the reaction apparatus of the present invention, the alkylation reactor may be any reactor, such as a fixed bed reactor, a batch tank reactor, a moving bed reactor, a fluidized bed reactor or a three-phase slurry bed reactor, and is preferably a fixed bed reactor. In the reactor, the reaction material may flow in an upward or downward manner. The reaction material can be fed from the top layer or the bottom layer of the catalyst or can be fed from different catalyst beds in a segmented mode.
The reaction apparatus of the present invention further comprises a line for recycling a portion of the material obtained by the hydroprocessing in the hydroprocessing section back to the reactor, a line for feeding a portion of the material obtained by the hydroprocessing in the hydroprocessing section to the fractionating column, and a line for recycling the alkylatable organic compound obtained by the fractionating in the fractionating column back to the alkylation reactor.
In the reaction device, the hydrogen at the top of the hydrogenation tower is recycled, 3-10% of the weight of distillate at the bottom of the hydrogenation tower is used as a product to enter a product rectifying tower for separation, and the rest materials are circulated to the inlet of the reactor.
In the reaction device, hydrogen is preferably introduced from the middle section of the hydrogenation tower, and the mass flow of hydrogen feeding is preferably 0.1-1% of the mass flow of the material flow at the outlet of the reactor. The material flow at the outlet of the reactor enters from the top side line of the hydrogenation tower, and the hydrogen ejected from the stripping tower returns to a hydrogen pipe network. The number of the plates of the hydrogenation tower is 60-150, and the reflux ratio is 5-40.
FIG. 1 is a schematic diagram of an apparatus and a basic material flow diagram according to an embodiment of the present invention.
Under the alkylation reaction condition, an alkylation reaction material (taking isobutane and butene as an example for alkylation reaction) enters a reactor to start reaction, a reaction outlet material enters a hydrogen stripping tower from the side line of the top of the tower, hydrogen is fed from the middle section of the tower and is contacted with an oil-containing material flowing from top to bottom, unreacted hydrogen is discharged from the top of the tower, a material containing alkylate is discharged from the bottom of the tower, most of a reaction material flow containing product alkylate and unreacted reactant such as isobutane circulates back to the inlet of the reactor through a pump 1, and a small part of the reaction product and the unreacted reactant enter a product fractionating tower to be separated. Isobutane separated at the top of the fractionating tower is circulated back to the inlet of the reactor by a pump 2, and alkylate oil is obtained at the bottom of the tower. Fresh reaction raw materials (a mixture of isobutane and butylene), an oil-containing material which is recycled to the inlet of the reactor after being hydrogenated and unreacted isobutane enter the reactor together to participate in reaction and regeneration.
The present invention will be further illustrated by the following examples, but the present invention is not limited to these examples.
In the examples and comparative examples, the alkylation process was carried out in a fixed bed reaction system containing 20ml of catalyst. The reaction system consists of the following three parts:
1. feeding and metering system: a mixture of isobutane and butene was fed into the reactor from a reaction feed tank using a precision metering pump (available from ISI inc., usa). The feed rate was measured by a precision electronic balance under the reaction feed tank.
2. Reaction system: the reactor can be filled with 20ml of catalyst, and the constant temperature area of the heating furnace ensures that the temperature of the catalyst bed is uniform and constant. The temperature of the catalyst bed in the reactor was controlled by a West temperature control instrument in the UK, and the pressure was controlled by a high precision pressure controller (available from TESCOM).
3. Separation and analysis system: the reaction product and unreacted materials firstly pass through a hydrogen tower, the tower bottom materials enter a buffer tank, the buffer tank samples the products of online chromatographic analysis, and the alkylate oil product is obtained by two-stage separation of high pressure and low pressure at the outlet of the buffer tank.
Example 1
This example illustrates the alkylation of isobutane with butenes according to the process of the present invention.
The alkylation reaction was carried out according to the scheme shown in FIG. 1.
10 g of Y molecular sieve catalyst (Changjin catalyst works, China petrochemical catalyst division) was weighed into a 20ml fixed bed reactor and a nitrogen stream was passed through. Raising the temperature and the pressure to the temperature and the pressure required by the reaction, pumping the mixed reaction raw material containing isobutane and butene according to the alkane-olefin ratio (the molar ratio of isoparaffin to olefin) required by the reaction material, and simultaneously closing the nitrogen flow. The reaction product is fed into a buffer tank after passing through a hydrogenation tower (the hydrogenation condition is that the mass flow of hydrogen feeding is 0.5 percent of the mass of material flow at the outlet of the reactor, the number of tower plates is 100, the reflux ratio is 20, the hydrogenation pressure is 2MPa, and the temperature at the top of the tower is 50 ℃), and a part of the reaction product and a part of unreacted isobutane are recycled to the inlet of the reactor by a high-pressure metering pump at the outlet of the buffer tank according to the reaction recycle ratio (defined as the ratio of the weight of the reaction product recycled to the inlet of the reactor to the weight of all the reaction products) and the alkane-alkene ratio. After the reaction was stabilized, the reaction product was periodically analyzed by gas chromatography.
The composition of the reaction feed is shown in Table 1.
TABLE 1
| Item | Butene material composition/%) | High purity isobutane/%) |
| Isobutane | 52.92 | 99.94 |
| N-butane | 8.69 | 0.06 |
| Butene of trans-butene | 21.15 | |
| N-butene | 2.11 | |
| Isobutene | 4.01 | |
| Cis-butenediol | 11.12 |
The alkylation reaction conditions are as follows: temperature 50 deg.C, pressure 3.0MPa, alkane/alkene 100 (mole ratio), circulation ratio 0.9, alkene weight space velocity 0.2 hr-1(ii) a The reaction results are shown in Table 2.
Comparative example 1
This comparative example illustrates the situation where the reactor outlet feed was directly recycled to the reactor inlet without passing through the hydroconversion column.
The catalyst, reaction mass and alkylation reaction conditions were the same as in example 1, but the reactor outlet material was directly recycled to the reactor inlet without passing through the hydroconversion column. The reaction results are shown in Table 2.
Comparative example 2
This comparative example illustrates a reaction process in which the reactor outlet material is not recycled.
The catalyst, reaction mass and reaction conditions were the same as in example 1, but the reaction product was not recycled back to the reactor inlet during the reaction. The reaction results are shown in Table 2.
TABLE 2
| Example 1 | 24h | 48h | 72h | 96h | 144h | 170h |
| C4Olefin conversion/%) | 100 | 100 | 100 | 100 | 100 | 100 |
| TMP selectivity/%) | 75.2 | 75.3 | 75.1 | 75.5 | 75.1 | 75.3 |
| Comparative example 1 | 24h | 48h | 72h | 96h | 100h | |
| C4 olefin conversion% | 100 | 100 | 100 | 97.5 | 95.5 | |
| TMP selectivity/%) | 75.3 | 71.3 | 65.2 | 55.1 | 52.3 | |
| Comparative example 2 | 24h | 48h | 72h | 80h | ||
| C4Olefin conversion/%) | 100 | 98.5 | 86.5 | 66.5 | ||
| TMP selectivity/%) | 75.1 | 63.5 | 50.8 | 48.5 |
As shown in Table 2, the product of the alkylation reaction is recycled to the inlet of the reactor after hydrogenation and enters the reactor together with the reaction material for alkylation reaction, and the product of the alkylation reaction is obtainedThe results of example 1 show that the catalyst activity (C) is after 170 hours have elapsed4Olefin conversion) was maintained at 100%. The selectivity to Trimethylpentane (TMP) in the alkylation product was maintained at 75%. The selectivity of the alkylation reaction remains unchanged. In the invention, the alkylation reaction product is subjected to hydrogenation operation to remove unsaturated hydrocarbon in the product and remove macromolecular covering on the surface of the catalyst at the same time, so that the clean surface of the catalyst is kept, and high alkylation reaction activity and selectivity are obtained.
As shown in Table 2, in comparative example 1, the catalyst activity (C) was measured after 96 hours of the alkylation reaction by directly recycling the reactor outlet material to the reactor inlet without passing through the hydroprocessed rectification column4Olefin conversion) started to be below 100% and the TMP selectivity decreased gradually, only 55% after 96 h. This result indicates that the catalyst has begun to deactivate.
As also seen from Table 2, comparative example 2 employed a method in which the reaction material was not circulated, and the catalyst activity (C) was exhibited after 48 hours had passed from the alkylation reaction4Olefin conversion) started to be below 100% and TMP selectivity decreased gradually, only 63.5% over 48 hours. This result indicates that the catalyst has begun to deactivate. The alkane-alkene ratio in the reaction materials which are not circulated in the reactor is lower, and the inactivation is quicker.
Example 2
The same recycle ratio as in example 1, 0.9, except that the reaction conditions were changed to: temperature 30 deg.C, pressure 5MPa, alkane/alkene 25 (mole ratio), olefin weight space velocity 1 hr-1. The reaction results are shown in Table 3.
Example 3
The same recycle ratio as in example 1, 0.9, except that the reaction conditions were changed to: temperature 150 deg.C, pressure 2MPa, alkane/alkene 10 (mole ratio), olefin weight space velocity 0.1 hr-1. The reaction results are shown in Table 3.
TABLE 3
| Example 2 | 24h | 48h | 72h | 96h | ||
| C4Olefin conversion/%) | 100 | 100 | 95.5 | 89.2 | ||
| TMP selectivity/%) | 70.2 | 69.3 | 58.1 | 52.6 | ||
| Example 3 | 24h | 48h | 72h | 96h | 144h | 170h |
| C4 olefin conversion% | 100 | 100 | 100 | 96.8 | 85.7 | |
| TMP selectivity/%) | 74.2 | 73.8 | 72.8 | 68.5 | 61.5 |
Example 4
The same as example 1, except that the hydrogenation conditions were such that the mass flow of hydrogen was 0.1% of the mass of the reaction outlet stream, the number of plates was 60, the reflux ratio was 5, the pressure in the hydrogenation was 3MPa, the operation temperature at the top of the column was 10 ℃ and the reaction results are shown in Table 4.
Example 5
The same as example 1, except that the hydrogenation conditions were such that the mass flow of hydrogen was 1% of the mass of the reaction outlet stream, the number of trays was 150, the reflux ratio was 40, the pressure in the hydrogenation was 0.5MPa, the operation temperature at the top of the column was 100 ℃ and the reaction results were as shown in Table 4.
Comparative example 3
The same as example 1, except that the hydrogenation conditions were such that the mass flow of hydrogen was 0.05% of the mass of the reaction outlet stream, the number of plates was 30, the reflux ratio was 55, the pressure in the hydrogenation was 5MPa, the operation temperature at the top of the column was 120 ℃ and the reaction results are shown in Table 4.
Comparative example 4
The same as example 1, except that the hydrogenation conditions were such that the mass flow of hydrogen was 1.5% of the mass of the reaction outlet stream, the number of plates was 200, the reflux ratio was 2, the pressure in the hydrogenation was 0.3MPa, the operation temperature at the top of the column was 5 ℃ and the reaction results are shown in Table 4.
TABLE 4
| Example 4 | 24h | 48h | 72h | 96h | 144h | 170h |
| C4Olefin conversion/%) | 100 | 100 | 100 | 100 | 100 | 100 |
| TMP selectivity/%) | 75.1 | 75.5 | 75.3 | 75.4 | 75.2 | 75.3 |
| Example 5 | 24h | 48h | 72h | 96h | 144h | 170h |
| C4Olefin conversion/%) | 100 | 100 | 100 | 100 | 100 | 100 |
| TMP selectivity/%) | 75.3 | 75.1 | 75.5 | 75.4 | 75.2 | 75.4 |
| Comparative example 3 | 24h | 48h | 72h | 96h | 120h | 144h |
| C4 eneConversion of hydrocarbons/%) | 100 | 100 | 100 | 100 | 95.5 | 85.8 |
| TMP selectivity/%) | 75.3 | 71.3 | 65.2 | 64.1 | 58.3 | 52.8 |
| Comparative example 4 | 24h | 48h | 72h | 96h | 144h | 170h |
| C4Olefin conversion/%) | 100 | 100 | 100 | 100 | 95.5 | 85.8 |
| TMP selectivity/%) | 75.1 | 72.8 | 68.2 | 65.1 | 58.3 | 52.8 |
Claims (15)
1. A solid acid alkylation process comprising contacting a reaction feed comprising an alkylatable organic compound and an alkylating agent under alkylation reaction conditions in the presence of a solid acid catalyst to form an alkylate, characterized in that the process comprises the steps of contacting an alkylation reactor outlet stream with hydrogen and separating the product, and recycling a portion of the separated hydrogen-free material back to the alkylation reactor.
2. The process of claim 1 wherein said alkylatable organic compound is a C4-C6 isoparaffin and said alkylating agent is a C3-C6 single bond olefin.
3. The process of claim 2 wherein said C4-C6 isoparaffin is isobutane and said C3-C6 single bond olefin is 1-butene and/or 2-butene.
4. The process of claim 1 wherein said solid acid catalyst is selected from the group consisting of zeolite molecular sieve catalysts, supported heteropolyacid catalysts, and SO4 2-Oxide super acidic catalyst, supported Bronsted-Lewis conjugated solid super acidic catalyst, ion exchange resin, Lewis acid treated oxide and Lewis acid treated molecular sieve catalyst.
5. The process of claim 4 wherein said zeolitic molecular sieve catalyst is X, Y or beta molecular sieve.
6. The method according to claim 2, wherein the alkylation reaction conditions are a reaction temperature of 10 to 350 ℃, a reaction pressure of 0.5 to 10.0MPa, a molar ratio of isoparaffin to single-bond olefin of 2 to 500, and a reactionThe weight space velocity of the single-bond olefin as the raw material is 0.05-20 hours-1(ii) a Preferably, the alkylation reaction conditions comprise a reaction temperature of 30-150 ℃, a reaction pressure of 2.0-5.0 MPa, a molar ratio of isoparaffin to single-bond olefin of 10-100, and a weight space velocity of the reaction raw material single-bond olefin of 0.1-1 hour-1。
7. The process of claim 1 wherein said reaction feed is fed in one portion from the top or bottom of the catalyst bed in the alkylation reactor or said reaction feed is fed in one portion from different catalyst beds in the alkylation reactor.
8. The process of claim 1 wherein said contacting of the alkylation reactor outlet stream with hydrogen is at a pressure of 0.5 to 3MPa and an overhead temperature of 10 to 100 ℃; preferably, the pressure is 1-3 MPa, and the tower top temperature is 50-100 ℃.
9. The process of claim 1 wherein the hydrogen-free feed is 90 to 97 weight percent of the feed recycled to the alkylation reactor.
10. The process according to claim 1, wherein the hydrogen gas has a mass flow rate of 0.1 to 1% of the mass flow rate of the reactor outlet stream.
11. A solid acid alkylation reaction device is characterized by comprising an alkylation reactor, a hydrogenation tower and a fractionating tower, wherein the alkylation reactor is connected with the hydrogenation tower, and the hydrogenation tower is used for contacting reaction products and alkylatable organic compounds led from the alkylation reactor with hydrogen to carry out hydrogenation treatment; the fractionating tower is used for fractionating the material led out from the tower kettle of the hydro-tower to obtain the alkylate oil.
12. The reactor apparatus according to claim 11 further comprising a line for recycling a portion of the hydroprocessed material in the hydroprocessor back to the reactor, a line for feeding a portion of the hydroprocessed material in the hydroprocessor to the fractionation column, and a line for recycling the alkylatable organic compound fractionated in the fractionation column back to the alkylation reactor.
13. The reactor apparatus of claim 11 wherein in said hydroprocessing column hydrogen is introduced from the mid-column section.
14. The reactor apparatus of claim 11 wherein the alkylation reactor is provided with an overhead sidedraw for directing an output stream from the alkylation reactor to the hydrogenation column.
15. The reactor according to claim 11, wherein the number of the plates in the hydrogenation column is 60 to 150 and the reflux ratio is 5 to 40.
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| CN114426888B (en) * | 2020-09-28 | 2023-10-13 | 中国石油化工股份有限公司 | Fixed bed alkylation reaction regeneration device and solid acid alkylation reaction and regeneration method |
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