Purge gas-based methanol production process

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to improved process of producing methanol from purge gas produced in basic methanol or ammonia synthesis. Process comprises dispensing compressed carbon dioxide into basic synthesis purge gas, heating resultant gas mixture to starting synthesis temperature, passing thus heated gas through methanol synthesis catalyst, cooling reacted gas, recovering condensed crude methanol, and separating non-condensed gas stream into return stream and purge stream, the former being designed for mixing with basic synthesis purge gas stream and passed to one or two circulation jet compressors. Circulation is effected by energy provide either by (i) pressure of basic synthesis purge gas, which is supplied to jet compressor and further dispensed into compressed carbon dioxide stream, or by (ii) pressure of compressed carbon dioxide, which is dispensed into jet compressor and then introduced into basic synthesis purge gas stream, or by (iii) pressure of basic synthesis purge gas and pressure of indicated compressed carbon dioxide, both being supplied to one or two jet compressors. Ammonia or methanol production purge gas is successfully used for production of methanol without utilizing additional hydrogen-containing streams.

EFFECT: reduced methanol production cost.

4 cl, 5 dwg, 1 tbl, 4 ex

 

The present invention relates to the field of chemical technology and can be used, in particular, in plants producing methanol and ammonia.

A method of producing methanol, as described in the application of the RF N 93054026, and presupposes the process of methanol synthesis, in which as the source of hydrogen containing gas is used purge gas ammonia production. The formation of methanol proceeds according to the following reactions:

The purge gas consists of hydrogen and inert impurities: methane, nitrogen, argon and ammonia. At the same time to ensure the synthesis of methanol in the purge gases for the synthesis of ammonia is dosed carbon dioxide in an amount such that the maximum use of hydrogen in the purge gas. Thus the value of factorial (f), representing the ratio f=(H2-CO2)/(CO2+CO)is 2.0-2.15. The main disadvantage of this method is low efficiency, which is due to the fact that the scheme is running, and not circulating. There is also known a method for the production of methanol, as described in patent US 5424335 and presupposes the process of methanol synthesis in two stages, one of which uses fresh synthesis gas, and the second step performs the synthesis of methanol from the purge gas is methanol synthesis the first step in running the scheme. The disadvantages of this method include

1. Low content of carbon monoxide and carbon dioxide in the vent gas, which leads to low production of methanol from these gases.

2. Flow diagram causes a small degree of actuation of the source reagents synthesis gas and a large amount of catalyst.

The closest to the technical nature of the claimed method is described in patent US 4226795. The method includes heating the purge gas to the initial temperature of the synthesis, the amount of gas leaked through the methanol synthesis catalyst, cooling the reacted purge gas, the release of the condensed methanol, the output from the system part neskondensirovannyh flow of purge gas and the circulation of the remaining part neskondensirovannyh flow of purge gas into the synthesis of methanol on the purge gases and different

use as a source of hydrogen containing gas purge gas ammonia production, methanol, etc.;

additional hydrogen containing gas with a lower pressure than the pressure of the purge gas, which is the purge gas other production, increasing the pressure of the second hydrogen-containing gas stream due to the energy of the purge gas in the jet compressor;

the dosage is of xadow carbon in the gas mixture to maintain the factorial in the range from 2:1 to 12:1.

To implement the circulation neskondensirovannyh flow of purge gas is used, the circulation compressor with the drive.

The disadvantages of this method include.

1. The need to use as a secondary raw material purge gas produced in other countries with a lower pressure than the main stream.

2. The additional cost of energy to drive the circulation of the compressor.

The technical purpose of this invention is the more efficient use of purge gas ammonia or methanol to obtain a methanol without additional hydrogen-containing streams.

The task is achieved through

1) the dosage of compressed carbon dioxide purge gas;

2) implementation of a process for the synthesis of methanol from a mixture of the purge gas ammonia or methanol with carbon dioxide in the circulation scheme;

3) use pressure purge gas main synthesis of ammonia or methanol or pressure compressed in the compressor of carbon dioxide for the implementation of the circulation through the jet compressor to install the methanol synthesis on the purge gases.

Summary of the invention in the method of producing methanol from the purge gas of the primary synthesis of ammonia or methanol, which includes

- dose is the formation in the purge gas is the primary synthesis of compressed carbon dioxide

- heating the obtained gas mixture to a starting temperature of synthesis,

- passing the heated gas through the catalyst for methanol synthesis,

the cooled reacted gas, the release of the condensed methanol,

- division neskondensirovannyh gas flow into two: the return and vent,

and is as follows: return neskondensirovannyh stream for mixing with the flow of purge gas main synthesis is referred to one or two circulating jet compressor and circulation exercise

a) either due to the energy-pressure purge gas main synthesis, served in a jet compressor, followed by the specified dosage in a stream of compressed carbon dioxide

b) or by the energy of the pressure in the compressor of carbon dioxide, the specified dosage which is carried out in a jet compressor with subsequent introduction into the flow of purge gas main synthesis,

in) or due to the energy-pressure purge gas main synthesis and energy pressure specified compressed in the compressor of carbon dioxide. Under the condition of equality of the pressure of the flows of the mixture of the flows is served in one jet compressor, and subject to inequality pressure of these threads each thread is served in individual inkjet whom the springs.

The multiplicity of circulation change in the range from 1.1 to 5.0, depending on the pressure of process gases: purge gas main synthesis and carbon dioxide. The higher the pressure of the process gas, the higher the ratio of circulation.

Carrying out the proposed method is illustrated in the accompanying simplified process diagrams (figures 1, 2, 3, 4, 5) in accordance with a preferred variant embodiment of the invention.

Option 1 (1)

The purge gas is the primary synthesis of ammonia or methanol (stream 1) under pressure 32-40 MPa is supplied to the jet compressor, position 9, it there is a circulating gas of the methanol synthesis on the purge gas (stream 2). The pressure of the mixed gas at the outlet of the jet compressor (flow 3) reaches 8-9 MPa.

Next to the stream 3 is dosed carbon dioxide, compressed in the compressor POS. 10 to the same pressure 8-9 MPa (flow 6). Flow 4 is sent to the Department of methanol synthesis, pos.11. From the Department of methanol synthesis is displayed methanol-raw (stream 8) and exhaust gas (stream 5). Next, from the exhaust stream output stream 7 as the purge gas to maintain a certain concentration of inert components in the cycle of synthesis. The remaining thread 2 returns in the jet circulation compressor.

Option 2 (2)

Carbon dioxide (stream 6), compressed in to the pressure, POS. 10, pressure 32-40 MPa is supplied to the jet compressor, position 9. In the jet compressor is also served circulating gas of the methanol synthesis on the purge gas (stream 2). The pressure of the mixed gas at the outlet of the jet compressor (flow 3) reaches 4.5-9.0 MPa. Further, the thread 3 is mixed with the purge gas main synthesis (stream 1) at a pressure of 4.5-9.0 MPa. Flow 4 is sent to the Department of methanol synthesis, pos.11.

From the Department of methanol synthesis is displayed methanol-raw (stream 8) and exhaust gas (stream 5). Next, from the exhaust stream output stream 7 as the purge gas to maintain a certain concentration of inert components in the cycle of synthesis. The remaining thread 2 returns in the jet circulation compressor.

Option 3 (3)

Carbon dioxide (stream 6), compressed in the compressor 10, to a pressure of 30-35 MPa, mixed with the purge gas flow of 1 production of ammonia or methanol under the same pressure and the mixture of gases is supplied to the jet compressor, position 9. In the jet compressor is also served circulating gas of the methanol synthesis on the purge gas (stream 2).

The pressure of the mixed gas at the outlet of the jet compressor (flow 3) reaches 4.5-9.0 MPa. Further, the thread 3 is sent to the Department of methanol synthesis, pos.11.

From the Department of methanol synthesis derived methane is l-raw (stream 8) and exhaust gas (stream 5). Next, from the exhaust stream output stream 7 as the purge gas to maintain a certain concentration of inert components in the cycle of synthesis. The remaining thread 2 returns in the jet circulation compressor.

Option 4 (5)

Carbon dioxide (stream 6), compressed in the compressor 10, to a pressure of 30-35 MPa, enters the jet compressor, pos.12. In the jet compressor, POS. 12, also serves a portion of the circulating gas of the methanol synthesis on the purge gases (stream 2A). From the jet compressor, POS. 12, enters the stream 3. Purge gases ammonia or methanol (stream 1) at a pressure different from the pressure of carbon dioxide, served in the jet compressor, POS. 13. It there is the remaining part of the circulating gas of the methanol synthesis on the purge gases (stream 26). From the jet compressor, POS. 13, extends thread 4. Streams 3 and 4 are mixed to form stream 9, which is sent to the Department of methanol synthesis, POS. 11. The pressure of the gas flow at the outlet of jet compressors must be the same that is caused by division of the flow 2 flows 2A and 2B. From the Department of methanol synthesis is displayed methanol-raw (stream 8) and exhaust gas (stream 5). Next, from the exhaust stream output stream 7 as the purge gas to maintain a certain concentration of inert components in the cycle of synthesis. The remaining stream 2 is divided into two streams 2A and 2B, which are returned in the jet compressors, position 12 and 13.

The results of calculations described above variants of the process are shown below in table 1. The invention is illustrated by the following examples.

Example 1 illustrates the circulation of motorized) (4)

Purge gas (stream 1) primary production of methanol has the following composition: CO - 9.97%, SN4- 8.95%, N2- 68.71%, CO2- 0.58%, Ar - 2.6% N2- 9.19%, consumption 5140 nm3per hour and a pressure of 5.0 MPa. The purge gas is mixed with compressed up to 5.0 MPa with carbon dioxide (flow 6) in the amount of 770 nm3/hour. The mixture of gases (stream 3) is supplied to the inlet of the circulation compressor, position 9, pre-mixed with the circulating gas (stream 2). The compressed coolant gas (stream 4) arrives in the Department of synthesis, pos.11. The circulation compressor with electric provides a multiplicity of circulation 4.5. From the Department of methanol synthesis is displayed methanol-raw (stream 8) 1.043 t/h and a residual gas (stream 5). Forth from the residual gas is separated purge gas (stream 7), the remaining gas (stream 2) is returned to the suction side of the circulation compressor. The power consumption for the compression of carbon dioxide and implementation of circulation equals 336 kW·h per tonne of methanol raw.

Example (1)

Purge gas (stream 1) primary production of methanol having the following composition: CO - 9.97%, SN4- 8.95%, N2- 68.71%, CO2- 0.58%, Ar - 2.6%, N2- 9.19%, consumption 5140 nm3per hour and a pressure of 40.0 MPa, served in the jet compressor, position 9, it there is a circulating gas of the methanol synthesis on the purge gas (stream 2) 14991 nm3per hour, which corresponds to the ratio of circulation 2.54. The pressure of the mixed gas at the outlet of the jet compressor (flow 3) reaches 9.0 MPa. Next to the stream 3 is dosed carbon dioxide (flow 6) in the amount of 770 nm3per hour and compressed to a pressure of 9.0 MPa. Flow 4 is sent to the Department of methanol synthesis, pos.11, where the formation of methanol. From the Department of methanol synthesis is displayed methanol-raw (stream 8) 1.578 t/h and the power consumption for the compression of carbon dioxide is 101 kW·h per tonne of methanol raw.

Example 3 (2)

Carbon dioxide in the amount of 770 nm3/HR (stream 6) is compressed in the compressor 10, to 35.0 MPa is supplied to the jet compressor, position 9, it there is a circulating gas of the methanol synthesis on the purge gas (stream 2) 23130 nm3per hour, which corresponds to the ratio of circulation 4.5. The pressure of the mixed gas at the outlet of the jet compressor (flow 3) reaches 5.0 Neprodumani gas (stream 1) primary production of methanol, having the following composition: CO - 9.97%, SN4- 8.95%, N2- 68.71%, CO2- 0.58%, Ar - 2.6%, N2- 9.19%, consumption 5140 nm3per hour and a pressure of 5.0 MPa, served in the gas mixture after the jet compressor, position 9. Flow 4 is sent to the Department of methanol synthesis, pos.11, where the formation of methanol. From the Department of methanol synthesis is displayed methanol-raw (stream 8) 1.043 t/h and the power consumption for the compression of carbon dioxide 290 kW·h per tonne of methanol raw.

Example 4 (3)

Purge gas (stream 1) primary production of methanol, which has the following composition: CO - 9.97%, SN4- 8.95%, N2- 68.71%, CO2- 0.58%, Ar - 2.6%, N2- 9.19%, consumption 5140 nm3per hour and a pressure of 40.0 MPa is mixed with the compressed to the same pressure carbon dioxide (flow 6) in the amount of 770 nm3/hour. The gas mixture is fed into the jet compressor, position 9, it there is a circulating gas of the methanol synthesis on the purge gas (stream 2) 26558 nm3per hour, which corresponds to the ratio of circulation 4.5. The pressure of the mixed gas at the outlet of the jet compressor (flow 3) reaches 9.0 MPa. Stream 3 is sent to the Department of methanol synthesis, POS. 11, where the formation of methanol. From the Department of methanol synthesis is displayed methanol-raw (stream 8) 1.859 t/h and when this is the power consumption for the compression of carbon dioxide is 183 kW· h per tonne of methanol raw.

As can be seen from examples 1, 2, 3, 4,

the use of circulation, organized by the energy of the compressed process streams in the Department of methanol synthesis on the purge gases, reduces the specific energy consumption per tonne of crude methanol in the range of from 15 to 70%,

energy use compressed up to 40.0 MPa of carbon dioxide and energy purge gases ammonia or methanol for gas circulation in the Department of synthesis increases removal of methanol, 18%,

at low pressure the main synthesis circulation synthesis purge gas, it is expedient to arrange due to the energy compressed in the compressor of carbon dioxide.

5140
Table 1
NameThe synthesis purge gasPressure: prodavec. gases/carbon dioxide, MPaThe consumption of air blast. gases in the synthesis nm3/hThe consumption of CO2nm3/hPressure synthesis, MPaThe multiplicity circulationConsumption Elektronnyi kW·h/t of crude methanolProduction. the crude methanol t/h
Example 1 given prototypeCirculation through the compressor ellektroprivodom5.0/5.07705.04.5336.01.043
Example 2

Option 1
Circulation due to the energy of purge gases40/9 .051407709.02.54101.01.578
Example 3

Option 2
Circulation at the expense of energy compressed in the compressor of carbon dioxide5.0/35.051407705.04.5290.01.043
Example 4

Option 3
Circulation due to the energy of purge gases and carbon dioxide40/4051407709.04.5183.01.859

1. A method of producing methanol from the purge gas of the primary synthesis of methanol or ammonia, including dosing in the purge gas is the primary synthesis of compressed carbon dioxide, heating the obtained gas mixture to the initial synthesis temperature, passing the heated gas through the methanol synthesis catalyst, cooling the reacted gas, the release of the condensed methanol and separation neskondensirovannyh gas stream two: return and purge, characterized in that the return flux is for mixing with a flow of purge gas main synthesis is referred to one or two circulating jet compressor and circulation carry out:

a) either due to the energy-pressure purge gas main synthesis, served in the jet compressor, followed by the specified dosage in a stream of compressed carbon dioxide

b) or by the energy of the pressure of compressed carbon dioxide, the specified dosage which is carried out in a jet compressor with subsequent introduction into the flow of purge gas main synthesis,

in) or due to the energy-pressure purge gas main synthesis and energy pressure specified compressed carbon dioxide, which is served in one or two of the jet compressor.

2. The method according to p. 1B, characterized in that under the condition of equal pressure purge gas primary production and carbon dioxide pressure of the mixture of the flows is served in one jet compressor.

3. The method according to p. 1B, characterized in that, subject to the inequality pressure purge gas primary production and carbon dioxide pressure of each stream is served in a private jet compressor.

4. The method according to claim 1, characterized in that the ratio of circulation is in the range from 1.1 to 5.0, depending on the gas pressure - purge gas main synthesis and carbon dioxide: the higher the gas pressure, the higher the ratio of circulation.



 

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