The way co-production of ammonia and methanol

 

(57) Abstract:

The invention relates to a method for joint production of ammonia and methanol. Installation for the combined production of ammonia and methanol includes the first primary partition of reforming and secondary reforming section, set in rows, to obtain a first gas phase comprising CO, CO2and H2that section of the synthesis of ammonia and the section of methanol synthesis. It further comprises a means for supplying methane and steam in the specified first primary reforming section, the second primary reforming section "exchange" type to obtain a second gaseous phase comprising CO, CO2and H2means for feeding methane and steam in the reaction zone, the connecting means between the said secondary reforming section and the second primary reforming section, a means for indirect heat exchange between the said first gaseous phase and the methane and steam in the second primary reforming section, the connecting means between the said second primary reforming section and the specified section of methanol synthesis and the connecting means between the said second primary reforming section and the specified section of the synthesis and methanol includes the stage of filing of methane and steam in the reaction zone, defined in the second primary reforming section. At the same time, the first gaseous phase is fed from the outside into the reaction zone of the second primary reforming section. Methane and steam interact through indirect heat exchange with the first gaseous phase to obtain a second gaseous phase comprising CO, CO2and H2. The first gaseous phase coming from the second primary reforming section, then served in the section of the ammonia synthesis, while the second gaseous phase is fed into the section of methanol synthesis. The invention improves proizvoditelnosti. 4 C. and 10 C.p. f-crystals, 1 Il.

The invention relates to a method for joint production of ammonia and methanol at the facility, including the first primary partition of reforming and secondary reforming section, located in the series section of the synthesis of ammonia and the partition of the methanol synthesis, the method comprising the stage of filing of methane and steam in the first primary reforming section, the interaction between methane and steam in the first primary reforming section and sequentially in the secondary reforming section with the first gaseous phase comprising CO, CO2and H2.

In the description below and the following formula gives the image the existing reactor, in order to improve its characteristics and to obtain, for example, greater productivity and/or greater degree of transformation and/or to reduce energy consumption.

In the description below and in the following claims, the term "synthetic section" means section of importance relating generally to the entire installation, or part thereof, relating to the production of ammonia and methanol and placed in operating condition by the movement of the stream bottom sections of the reformer.

In the description below and in the following claims, the term "methane" is understood as having a value, usually related to the raw material source of hydrogen and carbon, such as, for example, methane or a mixture of liquid and/or gaseous hydrocarbons such as natural gas and naphtha.

The present invention relates also to an apparatus for combined production of ammonia and methanol for carrying out the above method, as well as for the modernization of the installation of ammonia synthesis and for the modernization of the method for installing a joint production of ammonia and methanol.

As you know, there is a growing need in the field of joint production is more high performance at low production costs and capital investment and lower energy consumption.

To meet the above requirements has recently been proposed a joint venture in the field of synthesis of ammonia and methanol, where the flow of gas enriched in CO, CO2and H2emerging from the secondary section of the reformer installation of ammonia synthesis, is given in section synthesis of methanol production. Unreacted gas successively reactivated in section synthesis installation of ammonia.

Although in some sense the advantages of the place, the above methods have some disadvantages, the first of which is that the performance of the ammonia and the performance of methanol are interconnected and depend mainly on the quantities of methane and steam, which can be enjoyed in the reforming section.

In other words, as the total capacity of the plant operating in accordance with these methods, defined, essentially, the load power sections reforming, in a situation of full-scale operations increase productivity methanol inevitably causes approximately equivalent performance degradation of ammonia, and Vice versa.

This means that if it is desirable to obtain high performance and ammonia, and methanol is thus so they were able to support the load of reagents to achieve the desired performance. In addition, section synthesis of ammonia and methanol must be increased in size in order to meet any increased workload caused by the change in the production of methanol and ammonia.

Therefore, if you want high performance and production of ammonia and methanol production, should be provided with installation of joint production to ensure the above-mentioned methods, which reveals considerable structural complexity, high capital investment and production costs and high energy consumption.

Because of these disadvantages of previously known methods for joint production of ammonia and methanol found therefore, only a small application, despite the growing need in the industry.

The problem underlying the present invention is that provides a method for simultaneous production of ammonia and methanol, which is simple to execute and will allow to achieve high performance ammonia and methanol with low investments and the costs of production and low consumption EA ammonia and methanol aforementioned type, which is characterized by the fact that it comprises the stage of filing of methane and steam in a reaction zone defined in the second primary reforming section "exchange" type of filing of the first gaseous phase from the outside into the reaction zone to the second primary reforming section, the interaction between methane and steam in the reaction zone due to the indirect heat exchange with the first gaseous phase to obtain a second gaseous phase comprising CO, CO2and H2the filing of the first gaseous phase coming from the second primary reforming section, in the section of the ammonia synthesis and submit a second gaseous phase coming from the second primary reforming section, in the section of methanol synthesis.

In the description below and in the following claims, the term "primary reforming section "exchange" type" is understood as having the value of the primary section of the reforming production CO, CO2and H2in which the heat of reaction instead be provided by combustion of a fuel (e.g. natural gas or heavy gasoline), served by indirect heat exchange with a hot gas flow directed in this section. In this case, the flow of hot gas appears to be the first gaseous usual known in this technical field and are typically used in the synthesis of ammonia instead of the primary reformer is installed.

These reforming installation are inside the reaction zone, through which the gaseous reactants. The reforming reaction is possible due to the heat transfer of hot gas flowing from the outside into the reaction zone.

Reforming is an installation of this type are, for example, from a variety of pipelines, filled with a catalyst, the outer portion (side wall) is intended for the passage of hot gas, which gives the reaction heat by indirect heat exchange with a colder gas, which flows in pipelines (pipe surface), which take part in the heat exchange.

Reforming-install "exchange" type may also be provided with many adjacent chambers, alternately filled with catalyst, where the hot and cold gas flow through the empty chamber and the filling chamber, respectively. In this case, the camera is manufactured, for example, with mutually parallel walls or in the form of concentric cylinders.

Thanks to the method of the present invention is suitable is the ability to achieve independent production of ammonia and methanol, which allows to obtain high performance in a simple way, with low Capitaine the invention of high heat content in the first gaseous phase, emerging from the secondary reforming section, mainly used as heat of reaction in the production of the second primary reforming section of the second gaseous phase comprising CO, CO2and H2for the methanol synthesis process.

When implementing the object of the invention is a method for simultaneous production of ammonia at the facility, including the first primary partition of reforming and secondary reforming section, located in the series section of the synthesis of ammonia and the section of methanol synthesis, submit the methane and steam in the first primary reforming section, the interaction between methane and steam in the specified first primary reforming section, and then the secondary reforming section with the first gaseous phase comprising CO, CO2and H2moreover , the method also comprises the stage of filing of methane and steam in the reaction zone of the second primary reforming section "exchange" type of submission specified first gaseous phase outside the specified reaction zone in the specified second primary reforming section, the interaction in the specified reaction zone specified methane and steam by indirect heat exchange with the specified first gaseous phase to obtain a second gaseous phase, vkljucno section of the reformer in the specified section of the synthesis of ammonia, supply the specified second gaseous phase coming from the specified second primary reforming section in the specified section of methanol synthesis. Preferably, the temperature of the first gaseous phase is supplied to the second primary reforming section, was between 900oC and 1100oC. the Method may optionally include the stage of cooling of the specified second gaseous phase coming from the specified second primary reforming section, through indirect heat exchange with cooling water steam with high pressure and temperature, and/or additional stages of sampling at least part of this second gaseous phase coming from the specified second primary reforming section, and feeding at least part of this second gaseous phase specified in the first primary reforming section, and/or additional stages of selection purged gaseous flow comprising CO, CO2and H2emerging from the specified partition of the methanol synthesis, and delivery of the specified purged gaseous stream to the specified first primary reforming section.

When implementing the object of the invention is a plant for combined production of ammonia and methanol, comprising the gaseous phase, including CO, CO2and H2that section of the synthesis of ammonia and the partition of the methanol synthesis, the installation further added means for supplying methane and steam in the specified first primary reforming section, the second primary reforming section "exchange" type to obtain a second gaseous phase comprising CO, CO2and H2means for feeding methane and steam in a reaction zone defined in the specified second primary reforming section, the connecting means between the said secondary reforming section and the second primary reforming section for filing outside the specified reaction zone specified first gaseous phase, means for indirect heat exchange between the said first gaseous phase and the methane and steam in the second primary reforming section, the connecting means between the said second primary reforming section and the specified section for the methanol synthesis feed in the last second gaseous phase comprising CO, CO2and H2and connecting means between the said second primary reforming section and the specified section of the synthesis of ammonia for submission to the last mentioned first gaseous phase. It may also optionally sod is specified the second gaseous phase, emerging from the specified second primary reforming section, through indirect heat exchange with cooling water, and/or it further comprises a connecting means between the said second primary reforming section and the first primary reforming section for submission to last at least part of this second gaseous phase coming from the specified second primary reforming section, and/or it further comprises a connecting means between a specified section of methanol synthesis and the specified first primary reforming section for filing in the last purged gaseous flow comprising CO, CO2and H2emerging from the specified partition of the methanol synthesis.

When implementing the object of the invention is a method of upgrading your installation of combined production of ammonia and methanol comprising the first primary partition of reforming and secondary reforming section, set in rows, to obtain a first gas phase comprising CO, CO2and H2means for feeding methane and steam in the specified first primary reforming section, the section of the ammonia synthesis, the section of the synthesis of methanol, optionally enter a second primary partition reformiruemoi section of the reformer, the connecting means between the said secondary reforming section and the second primary reforming section for filing outside the specified first reaction zone a gaseous phase, means for indirect heat exchange between the said first gaseous phase and the methane and steam in the specified second primary reforming section, the connecting means between the said second primary reforming section and the specified section for the methanol synthesis feed in the last second gaseous phase comprising CO, CO2and H2and connecting means between the said second primary reforming section and the specified section of the synthesis of ammonia for submission to the last mentioned first gaseous phase.

When implementing the object of the invention is a method of upgrading your installation of combined production of ammonia and methanol comprising the first primary partition of reforming and secondary reforming section, located in a row to obtain a first gas phase comprising CO, CO2and H2means for feeding methane and steam in the specified first primary reforming section, the section of the ammonia synthesis, the section of the synthesis of methanol, optionally enter a second pelliconi second primary reforming section, the connecting means between the said secondary reforming section and the second primary reforming section for filing outside the specified first reaction zone a gaseous phase, means for indirect heat exchange between the said first gaseous phase and the methane and steam in the specified second primary reforming section, the connecting means between the said second primary reforming section and the specified section for the methanol synthesis feed in the last second gaseous phase comprising CO, CO2and H2and connecting means between the said second primary reforming section and the specified section of the synthesis of ammonia for submission to the last mentioned first gaseous phase.

When implementing both methods may further introduction section for cooling the specified second gaseous phase coming from the specified second primary reforming section, through indirect heat exchange with cooling water, and the section connected to the specified section of methanol synthesis, and/or supplementation of the connecting means between the said second primary reforming section and the first primary reforming section for soedinitelnoj means between a specified section of methanol synthesis and the specified first primary reforming section, intended for filing in the last purged gaseous flow comprising CO, CO2and H2emerging from the specified partition of the methanol synthesis.

Due to the aforementioned methods of upgrading an existing installation, it becomes possible to conduct the process of co-production of ammonia and methanol, easy to perform, able to achieve high performance and ammonia, and methanol at low production costs and capital investment and low energy consumption.

Characteristics and advantages of the present invention are further described his options below as an example and not limiting of the invention, with reference to the accompanying drawing.

The drawing shows a block diagram of the process of co-production of ammonia and methanol according to the present invention.

The drawing shows a block diagram illustrating the stages of the process of co-production of ammonia and methanol in accordance with the present invention.

This process allows you to simultaneously achieve high performance ammonia (for example, between 1000 and 2500 metric tons per day) and methanol (for example the dominant stage of the production process of ammonia.

In this part 10 blocks 11, 12 and 13 show, respectively, on the first primary partition of reforming and secondary reforming section and the section of the ammonia synthesis. The latter includes in addition to the actual sections of synthesis, high - and low-temperature sections of the CO conversion, the section of the Department of CO2and the section of the decomposition of methanol. The above-mentioned primary and secondary sections are catalytic reforming.

Item 20 indicates generally a portion of a block diagram, illustrating manufacturing process steps of methanol.

In this part of the 20 blocks 21 and 22 show respectively the second primary reforming section and the section of methanol synthesis. The latter also includes in addition to a valid section synthesis section of the condensation and separation of H2O and the cleaning section of methanol.

Mainly the second primary reforming section, as indicated by the block 21 is a section "exchange" type and preferably of the type equipped with an array of piping, filled with a catalyst, in which the reforming reaction.

The first primary reforming section, represented by block 11, is fed production line 1, which represents the first gas on the I installation of ammonia, for example 300-650oC.

Skip through the first primary partition of reforming and secondary reforming section (blocks 11 and 12), methane and steam contained in the first gaseous stream, interact with the first gaseous phase comprising CO, CO2and H2.

Line 2 represents the first gaseous phase coming from the secondary reforming section, shown by block 12. The temperature of the gas stream 2 is preferably between 980oC and 1050oC.

Mainly line 2 stream intersects with the side shell of the second primary reforming section, represented by block 21, where it is cooled from below by indirect heat exchange with a gaseous stream comprising methane and steam supplied side of the pipeline unit 21, and is shown by line 3 of the thread.

At the output of the second primary reforming section (block 21) of the gas stream 2 is fed into the section of the ammonia synthesis (13) at a temperature between 30oC and 600oC.

At the output of block 13 thread 2 contains mainly ammonia.

The gas flow, represented by the line 3 of the thread is fed to the second primary reforming section (block 21) at a temperature between 200oC and 6002and H2.

Line 4 of this thread shows a second gaseous phase coming from the second primary reforming section (block 21). The temperature of the gas stream 4 is usually between 700oC and 1000oC.

The gas stream 4 is fed into the section of methanol synthesis, represented by block 22. At the output of block 22 stream 4 contains mainly methanol.

Working conditions sections of the synthesis of ammonia or methanol (blocks 13 and 22, respectively), and the types of reactions taking place in them, are common to install synthesis of ammonia and methanol, respectively, well-known specialist in this field and therefore not described in more detail.

Pressure gas streams 1-4 are preferably between 1 bar and 60 bars.

In accordance with the co-production process according to the present invention, the first stream of methane and steam is fed to the first primary reforming section (block 11) and interacts in this section of the reformer and consistently in the secondary reforming section (blocks 11 and 12) with the first gaseous phase comprising CO, CO2and H2.

Thus, ammonia and methanol are produced in independent processes of synthesis, where the heat required for the reforming reaction of methane in the synthesis of methanol, mainly obtained through the use of high heat content in the gas stream exiting the secondary section of the reforming process of ammonia synthesis.

In accordance with another particularly preferred variant of the present invention, but not shown here, the co-production process includes the additional step of cooling the second gaseous phase (line 4 threads), leaving the second primary reforming section tours of steam, for example, between 5 bars and bars 130 and between 150oC and 550oC, respectively.

Conducting the process in this way, heat generated in the gas phase coming from the second primary reforming section, predominantly spent on the production of steam with high heat, which can be used depending on the need, for example, in other sections of the installation of combined production of ammonia and methanol.

The temperature of the gas stream 4, which is subjected to the above-mentioned cooling stage is preferably between 30oC and 300oC.

Heat a gas stream 4 out of the unit 21 may be returned for alternative pre-heating due to the indirect heat exchange of methane or other gaseous stream comprising methane and steam, to be submitted to the second primary reforming section.

In accordance with an alternative process of the present invention part of the second gaseous phase (line 4 flow out of the unit 21 can be mainly assigned to the first primary reforming section (block 11) process of ammonia synthesis. This allows you to tailor the performance of the production process madalsa in the synthesis of ammonia, with conservation of materials and energy.

In the drawing, this option is shown in broken lines with line 5 of the thread.

Installation of combined production of ammonia and methanol according to the present invention includes partitions, represented by the blocks 11-13 and 21-22 drawing.

On the input and between the sections constituting the above-mentioned unit, provide suitable feeding and connecting means, respectively, of the type known in the industry, such as pipes, pipelines and similar devices, represented schematically by lines 1-6 of the stream of drawing.

Inside the second primary reforming section, represented by block 21 are also provided with suitable means for indirect heat exchange between the gas streams 2 and 3. These means may include one or more heat exchangers.

Primarily installation according to the present invention also provides a cooling section (not shown) for cooling the gas stream 4 out of the unit 21, through indirect heat exchange with cooling water. The cooling section of this type may include, for example, the evaporator for the production of steam.

For stobtsy to line 3 or 4 thread preferably line 4 threads.

In fact, since the gas flowing through line 4, is usually very enriched in H2the above addition can improve the stoichiometric ratio of CO2/H2which leads to the improvement of conditions of methanol synthesis.

In accordance with the present invention a method of upgrading an existing installation of joint production of ammonia and methanol, comprising the first primary partition of reforming and secondary reforming section (blocks 11 and 12) located in the series section of the synthesis of ammonia (block 13) and the section of methanol synthesis (block 22), mainly provides the stage, providing the second primary reforming section (block 21) "exchange" type, including means suitable for indirect heat exchange, and providing the appropriate means for feeding the second primary reforming section (block 21)and the connection between the secondary reforming section and the second primary reforming section (blocks 12 and 21) in the relationship between the second primary reforming section and sections for the synthesis of ammonia and methanol (blocks 21, 13, 22).

A method of upgrading an existing installation of ammonia synthesis according to the present invention, provided is also a section of methanol synthesis (block 22).

Mainly in an alternative embodiment, the above methods of upgrading, not shown, a cooling section for cooling the gas stream 4 through indirect heat exchange with cooling water, to produce steam with a high level of heat, is provided between the blocks 21 and 22.

In addition, in accordance with another variant ways of modernization in accordance with the present invention mainly provides suitable connecting means between the first and second primary sections reforming (blocks 21 and 11) and between the section of methanol synthesis and the first primary reforming section (block 11). Thus, it becomes possible to remove excess CO, CO2and H2from the process of methanol synthesis and the synthesis of ammonia to facilitate methane load, which is sent to the reforming section installation of ammonia synthesis and, thus, achieve reduction of consumption of energy and raw materials.

In a particular situation, which is intended only to produce ammonia, the above methods of upgrading mainly help to increase the production sections of the reformer in relation to pre-existing installation of ammonia synthesis, and the huge benefits, achieved by the present invention. In particular, it provides a process of co-production of ammonia and methanol, simple in execution, able to achieve high performance of the synthesis of methanol and ammonia at low cost and capital investment and low energy consumption. In addition, in the case of modernization installation synthesis of ammonia or installation of combined production of ammonia and methanol, it becomes possible to achieve high performance methanol, maintaining at the same time, the constant performance of ammonia.

1. The way co-production of ammonia and methanol at the facility, including the first primary partition of reforming and secondary reforming section, located in the series section of the synthesis of ammonia and the partition of the methanol synthesis, the method comprising feeding methane and steam in the first primary reforming section, the interaction between methane and steam in the specified first primary reforming section, and then the secondary reforming section with the first gaseous phase comprising CO, CO2and H2, characterized in that it comprises the stage of filing of methane and steam in the reaction zone of the second primary reforming section "exchange" type of filing of kazankina, interaction in the specified reaction zone specified methane and steam by indirect heat exchange with the specified first gaseous phase to obtain a second gaseous phase comprising CO, CO2and H2filing specified first gaseous phase coming from the specified second primary reforming section, in the specified section of the ammonia synthesis, the supply of the specified second gaseous phase coming from the specified second primary reforming section, in the specified section of methanol synthesis.

2. The method according to p. 1, characterized in that the temperature of the first gaseous phase is supplied to the second primary reforming section, is between 900 and 1100oC.

3. The method according to p. 1, characterized in that it comprises the additional step of cooling the specified second gaseous phase coming from the specified second primary reforming section, through indirect heat exchange with cooling water steam with high pressure and temperature.

4. The method according to p. 1, characterized in that it includes an additional stage of sampling at least part of this second gaseous phase coming from the specified second primary reforming section, and feeding at least Chas p. 1, wherein it includes an additional stage of selection purged gaseous flow comprising CO, CO2and H2emerging from the specified partition of the methanol synthesis, and delivery of the specified purged gaseous stream to the specified first primary reforming section.

6. Installation for the combined production of ammonia and methanol, comprising the first primary reforming section 11 and a secondary reforming section 12, set in rows, to obtain a first gas phase comprising CO, CO2and H2tool 1 feed of methane and steam in the specified first primary reforming section 11, the section of the ammonia synthesis 13 and the partition of the methanol synthesis 22, characterized in that it further comprises a second primary reforming section 21 "exchange" type to obtain a second gaseous phase comprising CO, CO2and H2the means 3 for feeding methane and steam in a reaction zone defined in the specified second primary reforming section 21, the connecting means between the said secondary reforming section 12 and the second primary reforming section 21 to supply outside the specified reaction zone specified first gaseous phase, means DL is primary reforming section 21, the connecting means 4 between the said second primary reforming section 21 and the specified section of methanol synthesis 22 for filing at the last second gaseous phase comprising CO, CO2and H2and connecting means between the said second primary reforming section 21 and the specified section of the ammonia synthesis 13 for submission to the last mentioned first gaseous phase.

7. Installation according to p. 6, characterized in that it further comprises a section which is connected through a fluid with a specified section of methanol synthesis 22 for cooling the specified second gaseous phase coming from the specified second primary reforming section 21, by indirect heat exchange with cooling water.

8. Installation according to p. 6, characterized in that it further comprises a connecting means 5 between the said second primary reforming section 21 and the first primary reforming section 11 for submission to last at least part of this second gaseous phase coming from the specified second primary reforming section 21.

9. Installation according to p. 6, characterized in that it further comprises a connecting means 6 between the specified Cacciatore thread including CO, CO2and H2emerging from the specified partition of the methanol synthesis 22.

10. Upgrade installation of ammonia synthesis comprising the first primary reforming section 11 and a secondary reforming section 12, set in rows, to obtain a first gas phase comprising CO, CO2and H2the means 1 for feeding methane and steam in the specified first primary reforming section 11, the section of the ammonia synthesis 13, by introducing a partition of the methanol synthesis 22, the second primary reforming section "exchange" type 21, the means 3 for feeding methane and steam in the reaction zone of the specified second primary reforming section 21, the connecting means between the said secondary reforming section 12 and the second primary reforming section 21 to supply outside the specified reaction zone specified first gaseous phase, means for indirect heat exchange between the said first gaseous phase and the methane and steam in the specified second primary reforming section 21, the connecting means 4 between the said second primary reforming section 21 and the specified section of methanol synthesis 22 for filing at the last second gaseous phase comprising CO, CO the section of the ammonia synthesis 13 for submission to the last mentioned first gaseous phase.

11. Upgrade installation of combined production of ammonia and methanol, comprising the first primary reforming section 11 and a secondary reforming section 12, set in rows, to obtain a first gas phase comprising CO, CO2and H2the means 1 for feeding methane and steam in the specified first primary reforming section 11, the section of the ammonia synthesis 13, section of methanol synthesis 22, by introducing the second primary reforming section "exchange" type 21, the means 3 for feeding methane and steam in a reaction zone in the specified second primary reforming section 21, the connecting means between the said secondary reforming section 12 and the second primary reforming section 21 to supply outside the specified first reaction zone a gaseous phase, means for indirect heat exchange between the said first gaseous phase and the methane and steam in the specified second primary reforming section 21, the connecting means 4 between the said second primary reforming section 21 and the specified section of methanol synthesis 22 for filing at the last second gaseous phase comprising CO, CO2and H2and connecting means between the said second primary sec the phase.

12. The method according to p. 10 or 11, characterized in that the introducing section for cooling the specified second gaseous phase coming from the specified second primary reforming section, through indirect heat exchange with cooling water, and the section connected to the specified section of methanol synthesis 22.

13. The method according to p. 10 or 11, characterized in that impose the connecting means 5 between the said second primary reforming section 21 and the first primary reforming section 11 for submission to last at least part of this second gaseous phase.

14. The method according to p. 10 or 11, characterized in that impose the connecting means 6 between the specified section of methanol synthesis 22 and the first primary reforming section 11 for filing in the last purged gaseous flow comprising CO, CO2and H2emerging from the specified partition of the methanol synthesis.

 

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