The method of producing styrene and propylene oxide

 

Usage: petrochemistry. The inventive method involves the following stages: a) interaction of ethylene and benzene to form ethylbenzene; b) interaction of ethylbenzene with oxygen or air with the formation of gidroperekisi ethylbenzene; C) interaction of at least part of the received gidroperekisi ethyl benzene with propylene in the presence of an epoxidation catalyst with the formation of propylene oxide and 1-phenylethanol; g) digitately at least part of the obtained 1-phenylethanol in styrene in the presence of a suitable dehydration catalyst. When ethylene is used in stage (a), and propylene used in stage (C) at least partially derived from the exhaust gas installation fluid catalytic cracking unit containing C1and C2components. The technical result is a simplification of the holding means. 8 C.p. f-crystals, 1 tab., 2 Il.

The invention relates to method the joint production of styrene and propylene oxide.

This method is known in the art and is commonly called by way of styrene monomer/propylene oxide (MS/OP). Typically, the way MS/OP involves the following stages: (a) interaction of ethylene and benzene with education ativan is, though, at least part of the received gidroperekisi ethyl benzene and propene in the presence of an epoxidation catalyst with the formation of propylene oxide and 1-phenylethanol, and (d) dehydrating at least part of the obtained 1-phenylethanol in styrene in the presence of a suitable dehydration catalyst.

The aforementioned method MS/OP well known in the art. At the stage of (a) ethylbenzene is produced by the alkylation of benzene in the plant for ethylbenzene. Benzene can be obtained, for example, from installation to platforming, while the ethylene can be obtained from steam cracking installation. The alkylation reaction can be performed in various ways known in the art. For example, this reaction can be carried out as gas-phase or liquid-phase reaction using a catalyst based on the catalyst is aluminum chloride. In some ways the alkylation of benzene to produce ethylbenzene also use solid phosphorotioate catalysts or solid acid catalysts based on alumina, activated by boron TRIFLUORIDE. As a suitable method is a method known as the method Mobil/Badger. This method uses synthetic zeolite kata is moderate pressure. Getting ethylbenzene from ethylene and benzene over a zeolite catalyst is described in U.S. patent 4107224.

Stage (a) of the method can be carried out independently from steps (b)-(g) way, that is, at a different location. However, it is preferable to obtain ethylbenzene corresponded to obtain a styrene on stage (g), so that the setting for ethylbenzene was part of the way MS/OP or were close to MS/OP setup. Usually it is preferable to MS/OP installation combined installation for ethylbenzene.

At the stage of oxidation (b) liquid-phase oxidation of ethylbenzene in hydropeaking ethylbenzene occurs at a temperature of 100-160oWith, preferably 130-150oWith, and at a pressure 1-4 bar (100-400 kPa), preferably 2-3 bar (200 to 300 kPa). The oxidation is usually carried out using air as the gas-oxidant, but you can also use oxygen. The main side product obtained at this stage is acetophenone, which can be gidrirovanii in MS/OP method 1-phenylethanol, which is used in stage (d) to obtain styrene.

Under epoxidation () hydropeaking ethylbenzene interacts with propene, leading to the formation of propylene oxide and 1-penilee or heterogeneous catalyst. As homogeneous catalysts are often used molybdenum compounds, whereas as heterogeneous catalysts often use catalysts based on titanium on the carrier of silicon dioxide. Conditions for the epoxidation known in this area and usually include a temperature of from 75 to 150oC and pressure up to 80 bar (8000 kPa), while the reaction medium is in the liquid phase. Stemming the flow from the stage epoxidation first usually subjected to dividing processing to remove the formed propylene oxide, after which the remaining stream containing 1-phenylethanol, appropriately subjected to one or more subsequent separation treatments, among other things, removal of ethylbenzene to re-use at an earlier stage of the way. Retrieved ultimately a stream containing 1-phenylethanol, then subjected to dehydrating treatment stage (d).

Dehydration of 1-phenylethanol in styrene is also well known in this field. It can be performed both in the gas phase and in the liquid phase. Suitable dehydration catalysts include, for example, acidic substances, such as aluminum oxide, alkaline aluminum oxide, aluminum silicates and this is sup>oFor dehydration in the liquid phase and 210-320oWith, preferably, 280-310oIn case of dehydration in the gas phase. Pressure usually varies in the range from 0.1 to 10 bar (10-1000 kPa). In principle, stage (d) can be used any known method of dehydration.

In industrial MS/OP method propene used in stage (b) can be fed either from an external source, or you can get on the site MS/OP, usually in steam cracking installation (also commonly called ethylene installation). The last option is the preferred option and is used most often.

For method MS/OP, which includes stages (a) to(g) described above, requires equal amounts of ethylene and propene as starting materials. As a consequence, MS/OP installation are usually placed close to the ethylene units that produce as a necessary ethylene and propene. Accordingly, if you want to develop and create a new installation of MS/OP, this is usually either be located near the existing ethylene plant, which has spare capacity of ethylene and propene, or development should be included ethylene installation to ensure an adequate supply of ethylene and propene. T is unicipal accommodation choice for creating MS/OP installation and binds economy with ethylene installation. Accordingly, it would be advantageous if the ethylene and propene were served from an alternative source that does not have said drawbacks.

In the context of the present invention it has been found that when combining MS/OP method with liquid catalytic cracking (Zhytomyr cardboard factory) could overcome the above economic and logical barriers.

Accordingly, the present invention relates to method the joint production of styrene and propylene oxide, including the stage (a), (b), (C) and (d) described above, in which the ethylene used in stage (a), and propene used in stage (C) at least partially derived from Zhytomyr cardboard factory installation.

Typical installation Zhytomyr cardboard factory in the context of the present invention includes a reactor section and a processing section. In the reactor section is a real cracker, then graciously effluent stream is separated into various products in the processing section. Reactor section typically includes a reactor, a regenerator catalyst and athanasou section. The temperature in the reactor Zhytomyr cardboard factory installed liquid catalytic cracking typically less than 550oWith and, preferably, is in the range from 500 to 525oC.

Effluent stream from the reactor clubs is operating columns, in which is injected graciously effluent stream from the reactor section. Upper wrap this main distillation column contains low-boiling components, which are, mainly, C1-C4 hydrocarbons. In addition, small amounts of gases are present, such as hydrogen sulfide, carbonyl sulfide, hydrogen and nitrogen. This top shoulder straps are usually compressed and directed to the column absorption/distillation. Here the so-called flue gases containing mainly C1 and C2 components and a certain amount of hydrogen, nitrogen and sulfur components are removed and absorbed through the plant to remove sulfur components (usually amine installation) in the fuel gas system. Selected C3/C4 substances respectively sent to butnothing column, propanethiol column and, optionally, a separator propane/propene, where they perform the separation of the C4 stream, a propane stream and propenoic stream. All processing, since the separation in the main rectification column, form part of the processing section.

As described above, exhaust gases containing C1 and C2 components of the installation Zhytomyr cardboard factory, usually went to the fuel gas system. In the framework of the present invention, however, it is ash. Similarly, the propene used on stage epoxidation (C), is obtained from the separator propane/propene. However, setting Zhytomyr cardboard factory does not produce ethylene and propene in the desired ratio of 1:1. In the framework of the present invention may be used propene and ethylene obtained in the installation of Zhytomyr cardboard factory, together with ethylene and/or propene emanating from other sources, preferably located close to MS/OP setup, if the production of ethylene and/or propene install Zhytomyr cardboard factory is insufficient to meet the fashion needs of MS/OP in the ethylene and/or propene.

As indicated above, the ethylene used in stage (a), respectively obtained from the exhaust gas installation for fluid catalytic cracking units containing components C1 and C2. However, it is preferable that this exhaust gas, after passing it through amine installation, sequentially subjected to absorption/desorption processing for hydrogen, nitrogen and methane and processing for the extraction or hydrogenation of acetylene before you can send the resulting stream containing ethane and ethylene, in the device for producing ethylbenzene.

It was found that for purposes of the present invention is particularly advantageous that the zeolite catalyst, suitable catalysts based on ZSM-5, and to ethylbenzene and the remaining ethane subsequently allocated.

It was found that if ethylene is produced in the reactor section of the installation Zhytomyr cardboard factory, not enough to satisfy the needs of ethylene way MS/OP, it is very useful to make the remaining part of ethylene in one or more of the cracking furnace, which serves ethane and optionally propane obtained in the reactor section of the installation fluid catalytic cracking. Thus, C2 and C3 products, get in the way Zhytomyr cardboard factory, optimally used to create a supply of ethylene to install ethylbenzene. Ethane obtained in the Zhytomyr cardboard factory setting, can be made directly to the cracking furnace (the furnace). However, it is preferable to send the ethane in the form of a stream of ethane/ethylene in the plant for the production of ethylbenzene, where the ethylene interacts with benzene, leading to ethylbenzene. The remaining ethane separated from the installation for the production of ethylbenzene and then served in the cracking furnace(the furnace).

If the ethane from the installation Zhytomyr cardboard factory in itself does not provide sufficient additional after ethylene cracking furnaces(furnaces) for supply of ethylene, you can add the ethane from Vespene way MS/OP, feed in the cracking furnace(the furnace) may also contain propane, isolated from the installation fluid catalytic cracking, optionally supplemented by an external propane or even Bhutan. It will be clear that the required external ethane and/or propane, if it is necessary for the fashion needs of MS/OP in the ethylene and/or propene.

For optimal use of the section processing installation Zhytomyr cardboard factory and, consequently, to increase the overall efficiency of the method, it is preferable that the resulting stream from the cracking furnaces(furnaces) containing ethylene and, optionally, propene, processed in the processing section installation for fluid catalytic cracking with resultant stream from the reactor section installation for fluid catalytic cracking. Mentioned effluent stream from the cracking furnaces(furnaces) typically contains hydrogen, methane, non-ethane and heavier components in addition to the large number of ethylene. If the furnace(the furnace) enter propane mentioned resulting stream contains, in addition, propene, and unconverted propane and heavier components. So, stemming the flow of the furnace mixed with kreiranim resulting from reactor unit sections Zhytomyr cardboard factory before it is input to the processing section removes any impurities and methane, formed in the cracking furnaces.

It will be clear that the unification of the Zhytomyr cardboard factory installation with the way MS/OP according to the present invention is especially effective in the case when installing MS/OP needs to build simultaneously with the installation of Zhytomyr cardboard factory in the same place as it gives the ability to optimally integrated with the overall design. Alternatively, can also be effective, although usually smaller than in the above case, to construct a facility MS/OP in that place, where is already setting Zhytomyr cardboard factory.

Further, the invention is illustrated in Fig. 1 and 2. In Fig. 1 presents the General idea underlying the present invention. In Fig. 2 schematically shows a particularly preferred way of combining Zhytomyr cardboard factory installation and setup for ethylbenzene for the purpose of the present invention.

In Fig. 1 filing Zhytomyr cardboard factory (for example, heavy distillates) introduced in section 2 reactor Zhytomyr cardboard factory. Subsequently, the resulting stream 3 reactor process in the processing section 4, receiving stream 5 ethylene and propene stream 7. The flow of ethylene 5 is introduced into the installation ethylbenzene 9, optional with additional ethylene 6 from an external source, together with a stream of benzene 17. Then containing ethylbenzene stream 10 is sent to oxidative installation 11, where AA-oxidant. The resulting GPIB leaves oxidative installation 11 as stream 12 and is directed in the installation epoxidation 13, where it interacts with propene from a stream of propene 7 and, optionally, with propene 8 from an external source, which leads to the formation of propylene oxide 19 and 1-phenylethanol 14. Thread 1-phenylethanol 14 turn in the installation digitately 15 in styrene 16 and water 20.

In Fig. 2 stemming the flow 2 of the reactor section 1 Zhytomyr cardboard factory is injected into the main distillation column 3. Top zipper 4, derived from the main distillation column 3, is fed into the absorption column/rectification 5, where it is divided into the flow of exhaust gas 7 and C3/C4 stream 6. The off-gas flow 7 is directed through the amine 8 installation (for removal of sulfur components), installation of absorption/desorption 10 (removal of hydrogen, nitrogen and methane, to avoid the accumulation of these components in the process) and installing 13 removing acetylene, or hydrogenation in the installation of ethylbenzene 15. Stemming the flow of amine 8 installation essentially free from sulfur components, whereas the stream 12 exiting the installation of absorption/desorption 10, free from nitrogen, NOx, hydrogen and methane, which are all combined in stream 11. Flow 14 exiting set is free of ethylbenzene 15, where it is converted into ethylbenzene, exiting as stream 16, which should be directed in the installation oxidation method MS/OP (not shown). C3/C4 stream 6 is sent to butnothing column 20, which emit the upper shoulder 21 of butane/C3. This top shoulder straps 21 are served in propanethiol column 22 where it is separated into a stream of butane 23 and C3 stream 24, consisting mainly of propane and propene. Other components present in minor quantities, are methylacetylene and PROPADIENE (MA/PD) formed in the cracking furnaces(furnaces) 18, and sulfur components. Therefore, C3 stream 24 is passed through an amine installation of 25, after which desulfuromonas stream 26 is passed through installing 27 removing MA/PD, or hydrogenation, receiving a stream of propane/propene 28. This flow of propane/propene 28 is divided into a stream of propene 30 and the flow of propane 31 in the separator propane/propene 29. The propene stream 31 can directly be sent to the installation epoxidation method MS/OP (not shown). The flow of propane 31, optional with additional propane 32, together with atanderson flowing stream 17 installation ethylbenzene 15. This flowing stream 17 can be supplemented by external ethane 33. After that objdirectory stream 19, containing ethylene/propene, combined with the ensuing thread 2 reactor section Zhytomyr cardboard factory, and thus, optimal use of end sections Zhytomyr cardboard factory, already available, or you want to install. Ethylene from recerving discharge flow 19 in the end ends in a stream of ethylene/ethane 14, while propene ends in the flow of propene 30.

Further, the invention is illustrated by the following example without limiting the scope of the invention to this specific embodiment.

An example of the Unification of Zhytomyr cardboard factory installation and setup MS/OP, as shown in Fig. 2, is performed with the use of Zhytomyr cardboard factory installation 1 with the performance of the conversion of raw materials 6000 tons per day. Use three conventional conversion cracking furnace 18. For management of large-scale MS/OP installation developed by the United way, which requires the same number (12.5 tons/hour of ethylene and propene.

In the table of amounts of hydrogen, nitrogen, methane, acetylene, ethane, ethylene, propane and propene in different threads of a process, numbered as shown in Fig. 2, given in tons per hour (t/h).

As can be seen from the table, an integrated part of the way Zhytomyr cardboard factory and how MS/OP is the required amount of ethylene (12.5 t/h:p the epoxidation installation MS/OP (not shown in Fig. 2) with the required number of propene.

Thus, it is possible to see that the integration of Zhytomyr cardboard factory installation and setup MS/OP, in accordance with the present invention, has a very good opportunity without the need to install full steam cracking for submission of the required ethylene and propene.

Claims

1. The way the joint production of styrene and propylene oxide, comprising the stage of: a) interaction of ethylene and benzene to form ethylbenzene, interaction of ethylbenzene with oxygen or air, with the formation of gidroperekisi ethylbenzene, interaction, at least part of the received gidroperekisi ethyl benzene with propylene in the presence of an epoxidation catalyst with the formation of propylene oxide and 1-phenylethanol, and d) dehydrating at least part of the obtained 1-phenylethanol in styrene in the presence of a suitable dehydration catalyst, and ethylene used in stage (a) and propylene, used in stage (C) at least partially provided with liquid catalytic cracking.

2. The method according to p. 1, in which the ethylene used in stage (a), is obtained from the exhaust gas installation liquid catalytic cu is placed through amine installation sequentially subjected to absorption/desorption treatment to remove hydrogen, nitrogen and methane, and processing for removal of acetylene, then the resulting stream containing ethane and ethylene, is directed to an installation for production of ethylbenzene.

4. The method according to p. 3, in which the plant for the production of ethylbenzene stream containing ethane and ethylene in contact with benzene in the presence of a zeolite catalyst, and ethylbenzene, and the remaining ethane allocate.

5. The method according to any PP.1-4, in which one part of ethylene used in stage (a), get in the reactor section of the installation fluid catalytic cracking, and the other part of ethylene receive in one or more of the cracking furnace, which serves ethane and optionally propane obtained in the reactor section of the installation fluid catalytic cracking.

6. The method according to PP.4 and 5, in which ethane is first sent as a stream of ethane/ethylene in the plant for the production of ethylbenzene, then the remaining ethane separated from the installation for the production of ethylbenzene and served in the cracking furnace (the furnace).

7. The method according to p. 5 or 6, in which the flow supplied to the cracking furnace (the furnace), also contains propane, isolated from the installation fluid catalytic cracking, and, optionally, supplemented by external ethane and/or propane.

8. The method according to l the flax, handle section processing installation fluid catalytic cracking together with the exhaust flow reactor unit sections of a fluid catalytic cracking.

9. The method according to any of the preceding paragraphs, in which the temperature of the reactor in the reactor section of the installation fluid catalytic cracking is less than 550oWith, preferably 500-525oC.

 

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2 dwg, 1 tbl, 5 ex

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