Synthetic method for ammonia production

FIELD: industrial inorganic synthesis.

SUBSTANCE: process comprises passing nitrogen and hydrogen-containing synthesis gas stream through three stacked catalyst beds, wherein catalyst is based on iron with magnetite as principal constituent, which is reduced during the process until catalytically active form of alpha-iron is produced. Above-mentioned synthesis gas stream is obtained by combining stream directly supplied onto first catalyst bed with another stream, which is preheated via indirect heat exchange with products exiting first and second catalyst beds, whereupon product is recovered. Method is characterized by that gas under treatment is passed through middle catalyst bed at volume flow rate between 0.65 and 2.00 value of volume flow rate, at which gas under treatment is passed through upper catalyst bed, volume ratio of middle catalyst bed to upper catalyst bed lying preferably between 0.5 and 1.5.

EFFECT: increased yield of product.

2 cl, 1 dwg, 1 tbl

 

The present invention relates to a process for the production of ammonia, particularly to a method of catalytic produce ammonia from synthesis gas containing hydrogen and nitrogen.

Known way catalytic produce ammonia, including the stage of filing of the original stream of synthesis gas containing hydrogen and nitrogen, in the form of three streams in the reactor, containing three layers of catalyst, placed one on top of another, heating the first stream by indirect heat exchange with the product stream leaving the last layer of the catalyst, followed by the subsequent introduction of a second stream, feeding the combined stream, thus obtained, in the first layer of the catalyst with subsequent transmission of the specified thread through all three layers of catalyst, heating the third stream by indirect heat exchange with the product stream leaving the first and second layers of the catalyst, and then adding to the combined stream, which is introduced into the first catalyst bed, and the selection of the final product, and the catalyst layers contain a catalyst based on iron with magnetite as the main part, which restore during the process to catalytically active form of alpha-iron (see European patent application EP AND 000611, CL 01 1/4, 29.12.1999).

Reactor for carrying out the known method comprises three layers ka is alistore, located on top of each other, the line for supplying a source of synthesis gas containing hydrogen and nitrogen, three heat exchanger, one of which is located between the output from the upper layer of the catalyst and the entrance in the middle layer of the catalyst, the other is located between the output from the middle layer of the catalyst and the entrance to the lower layer of the catalyst, and the third heat exchanger is on the line for removal of the final product, is attached to the exit of the lower catalyst layer, and the first line for supplying a source of synthesis gas directly connected to the entrance at the top of the catalyst bed, a second line for supplying a source of synthesis gas is attached to the first line through the third heat exchanger, and a third line for supplying a source of synthesis gas passes through the second and first heat exchangers and then attached to the first line for supplying a source of synthesis gas.

The purpose of the invention is to increase savings ammonia production by simplifying technology and increase product yield.

To reach this aim method and reactor according to the invention, hereinafter described in detail here.

The method according to the invention includes the stage of passing a flow of synthesis gas containing nitrogen and hydrogen, through three layers of catalyst, placed one on top of another, which contain the catalyst based on jelly is and with magnetite as a main component, recovered during the process to catalytically active form of alpha-iron, and the specified stream to the synthesis gas is produced by combining stream, which is fed directly to the first layer of the catalyst, with another thread that is pre-heated by indirect heat exchange with the products leaving the first and second catalyst layers, and the selection of the final product, and the process is characterized by the fact that the processed gas is passed through the middle layer of the catalyst bulk velocity component from 0.65 to 2.00 from the volumetric rate at which the processed gas passes through the top layer of the catalyst.

According to preferred features of the reaction is carried out at the volume ratio between the average catalyst layer and the upper layer of the catalyst is between 0.5 and 1.5.

The reactor according to the present invention contains three catalyst layer located on top of each other, the first heat exchanger located between the output from the upper layer of the catalyst and the entrance in the middle layer of the catalyst, a second heat exchanger located between the output from the middle layer of the catalyst and the entrance to the lower layer of the catalyst, the first line for supplying a source of synthesis gas containing hydrogen and nitrogen is attached directly to the entrance of the upper layer of the catalyst, a second line for podcietego synthesis gas and subsequent transmission through the first and second heat exchangers, which is connected to the first line, and the line for removal of the final product, is attached to the exit of the lower layer of the catalyst, and the reactor is characterized by the fact that the line for removal of the final product is directly connected to the output of the lower catalyst layer.

According to preferred features of the invention, the volume ratio between the average catalyst layer and the upper layer of the catalyst is between 0.5 and 1.5.

The invention is further illustrated in the drawing, represents a simplified flow diagram of the proposed method, carried out in the reactor according to the invention.

The reactor 1 contains three catalyst layer located on top of each other, that is, the upper catalyst layer 2, the middle layer of the catalyst 3 and the bottom layer of the catalyst 4. Each catalyst bed contains a catalyst based on iron with magnetite as the main part, which restore during the process to catalytically active form of alpha-iron. The volume ratio between the average catalyst layer and the upper layer of the catalyst is between 0.5 and 1.5.

In addition, the reactor 1 contains lines 5, 6, 7 for the filing of the original synthesis gas containing hydrogen and nitrogen, lines 6 and 7 connected to the line 8, is attached to the inlet of the catalyst layer 2, and line 9 for removal of the final product p is of soedineni to the exit of the catalyst layer 4. The catalyst layers 2-4 are interconnected by lines 10 and 11. In line 10 is first heat exchanger 12, and line 11 is supplied to the second heat exchanger 13.

In the operation of the invention the source of the synthesis gas for the synthesis of ammonia is injected through lines 5, 6 and 7 in the reactor for the synthesis of ammonia 1. Fresh synthesis gas is passed through lines 6 and 8 in layer 2 and partially converted into layer 2. Partially converted synthesis gas is then passed in line 10 successively through the layers 3 and 4. When passing through these layers of nitrogen and hydrogen in the stream react exothermically, turning into ammonia. The exiting product stream enriched in ammonia, divert through line 9 from the reactor 1.

As noted here previously, the reaction between hydrogen and nitrogen proceeds exothermically in the catalyst, and the temperature of the processed stream increases. Due to thermodynamic reasons the temperature of the recycle stream in line 10 must be lowered before it is introduced into the layers 3 and 4. Therefore, the stream is cooled in heat exchangers 12 and 13 indirect heat exchange with a source of synthesis gas flowing in line 7 through the heat exchangers 13 and 12.

When passing through the heat exchangers 13 and 12 original synthesis gas in line 7 is heated by indirect heat exchange, as described above. The flow of heated raw material is then combined with a stream of fresh synthesis gas fed through line 6,and the combined stream is passed through line 8 into the top layer of the catalyst 2. The temperature of the combined stream is regulated addition of cold flow through the line 6.

In the above reactor, the reaction temperature in the first 2 and second 3 layers of the catalyst is determined by the flux ratio between the flows in lines 6 and 7. The temperature of the fresh synthesis gas in line 2 monitors the temperature at the inlet in the bottom layer of the catalyst 4.

According to the invention the processed gas is passed through the middle layer of the catalyst bulk velocity component from 0.65 to 2.00 from the volumetric rate at which the processed gas is passed through the top layer of the catalyst. In addition, the volume ratio between the average catalyst layer and the upper layer of the catalyst support is between 0.5 and 1.5.

The invention is further illustrated by the following example.

Example

The reactor, which is shown in the drawing and are explained in detail in the description above, with a fixed amount of casing that can withstand the pressure, operated at four different volumetric relationship between the upper and middle layers of catalyst in the reactor. In the experiments the volume ratio of the upper and middle layers of the catalyst is between 0.5 and 3.0. The volumetric rate corresponding to the processed gas was regulated accordingly. For each volume relations conducted the first experiment, by which establish ivali temperature at the entrance in the middle catalyst layer ("layer 2" in the following table, where layer 1 is the top layer of the catalyst) to obtain the maximum yield of product. Then, when the working temperature above and below the optimum was determined yield for each volume relationship. The above conditions and the results obtained thereby are shown in the table below.

To compare the effects of variations in temperature on the product yield for each volumetric relation with yield at the optimum temperature, the output at the optimal temperature is taken for 100%.

Table
Deviation from Optim. temperature input-20-16-110111620
ADJ. PR-VA., t/A.
Layer 2/layer 1=0,501539,31541,91544,41547,01544,31541,21538,0
Layer 1/layer 2=0,801543,41547,01550,61554,21550,61546,71542,7
Layer 2/layer 1=1,001543,4154,9 1552,61557,01552,71548,01543,4
Layer 2/layer 1=1,501538,41544,61550,91557,11551,41545,91541,2
Layer 2/layer 1=2,001524,01534,51543,91553,01547,41541,81533,6
Layer 2/layer 1=3,001498,61510,61522,71543,01525,21517,01509,4
ADJ. PR-VA., t/A.
Layer 2/layer 1=0,50the 98.999,099,299,499,299,098,8
Layer 1/layer 2=0,80of 99.199,499,699,899,699,3of 99.1
Layer 2/layer 1=1,00of 99.199,499,7100,099,799,4of 99.1
Layer 2/layer 1=1,5098,899,299,6100,099,699,3
Layer 2/layer 1=2,0097,998,699,299,799,499,098,5
Layer 2/layer 1=3,00of 98.297,0of 97.898,598,097,496,9

As can be seen from the above results, the decrease in the yield of the product when the deviation from the optimal operating temperature in the middle layer of the catalyst is significantly less in the reactor or process, with the size distribution of the catalyst in the middle and upper layers is between 0.5 and 1.5 according to the invention, compared with the results obtained when using the reactor and process, working with the appropriate volume ratio of the catalyst is between 2.0 and 3.0, which is known in the art and typically used in the ammonia industry. As a further advantage, the product yield is increased when the size of the top and middle layers of the catalyst according to the invention have the above-mentioned volume ratio of between 0.5 and 1.5. When the volume ratio of between 1.0 and 1.5 yield in tons per day under optimal conditions of temperature by approximately 2% higher compared to the optimal solution obtained by commonly used volumetric ratio of catalyst to 3.0.

1. Way catalytic the ski produce ammonia, including the stage of passing a flow of synthesis gas containing nitrogen and hydrogen, through three layers of catalyst, placed one on top of another, which contain a catalyst based on iron with magnetite as the main part, which restore during the process to catalytically active form of alpha-iron, receipt flow synthesis gas Association flow, which is fed directly to the first layer of the catalyst, with another thread that is pre-heated by indirect heat exchange with the products leaving the first and second catalyst layers, and the selection of the final product, characterized in that the recycle gas is passed through the middle layer the catalyst in flow rate from 0.65 to 2.00 volume rate at which the processed gas is passed through the upper catalyst bed.

2. The method according to claim 1, characterized in that the reaction is carried out at the volume ratio between the average catalyst layer and the upper layer of the catalyst is between 0.5 and 1.5.



 

Same patents:

FIELD: chemical industry; production of ammonia.

SUBSTANCE: the invention is pertaining to the process of synthesis of ammonia, in particular to improvement of the process of cleanout synthesis of the gas added into the catalytic reactor for substitution of the reacted synthesis gas. The method of synthesis of ammonia provides for compression of the synthesis gas containing hydrogen and nitrogen in a many-stage centrifugal compressor. On the first stage of this compressor the synthesis gas is compressed up to the pressure making from approximately 800 up to 900 pounds per a square inch - (56-63)·105 Pa, withdraw from this stage and cool, and also dehydrate by a contact to a liquid ammonia in a dehydrator. Then the cooled and dehydrated synthesis gas is fed back in the compressor and bring it on the second stage. The installation for realization of this process contains a centrifugal compressor supplied with the synthesis gas outlet, that connects the synthesis gas discharge outlet from the first stage of the compressor with the synthesis gas inlet in the dehydrator, and also an intermediate inlet of the synthesis gas connecting by a hydraulic link the inlet of the second stage of the compressor with the synthesis gas discharge (outlet) from the dehydrator. Due to the intermediate cooling and a dehydration the compressor rate is lowered, and due to favorable effect of the dehydrator on the last two stages of the compressor a significant saving of the consumed power is also achieved. The additional saving of the consumed power is possible due to decreased need of chill in the closed contour of the synthesis process.

EFFECT: the invention ensures a significant saving of the consumed power for the synthesis process in the installation.

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FIELD: inorganic synthesis catalysts.

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FIELD: heat power and chemical industries, applicable in production of ammonia.

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FIELD: industrial inorganic synthesis.

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2 cl, 1 dwg, 1 tbl

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EFFECT: the invention ensures solution of the problem of the ammonia synthesis efficiency.

8 cl, 1 ex, 2 tbl, 2 dwg

FIELD: chemical industry; installations and the methods of production of the synthesis-gas from the natural gas.

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EFFECT: the invention ensures the increased profitability of the installation due to production at one installation of several products.

15 cl, 1 dwg, 1 tbl

FIELD: inorganic synthesis catalysts.

SUBSTANCE: ammonia synthesis catalyst is based on ruthenium on carrier of inoxidizable pure polycrystalline graphite having specific BET surface above 10 m2/g, said graphite being characterized by diffraction pattern comprising only diffraction lines typical of crystalline graphite in absence of corresponding bands of amorphous carbon and which graphite being activated with at least one element selected from barium, cesium, and potassium and formed as pellets with minimal dimensions 2x2 mm (diameter x height). Catalyst is prepared by impregnating above-defined catalyst with aqueous potassium ruthenate solution, removing water, drying, reduction to ruthenium metal in hydrogen flow, cooling in nitrogen flow, water flushing-mediated removal of potassium, impregnation with aqueous solution of BaNO3 and/or CsOH, and/or KOH followed by removal of water and pelletizing of catalyst.

EFFECT: increased activity of catalyst even when charging ruthenium in amount considerably below known amounts and increased resistance of catalyst to methane formation.

12 cl, 1 tbl

FIELD: chemical industry; methods and devices for production of ammonia from the synthesis gas.

SUBSTANCE: the invention is pertaining to the method and installation for production of ammonia from the synthesis gas. The method of production of ammonia provides for the catalytic reaction of the synthesis gas contracted in the appropriate compressor having several stages, each of which has the inlet and the outlet for the synthesis gas. The synthesis gas is purified by the liquid ammonia from contained in it water and carbon dioxide. At that at purification of the synthesis gas use the gas-liquid mixer, which is connected on the one hand to the outlet of the first stage of the compressor, or to the outlet of the intermediate stage of the compressor, and on the other hand - with the inlet of the second stage located behind the first stage, or with the inlet of the intermediate stage of the compressor, and has the section of the certain length with diminishing cross-section. Into the mixer in the axial direction feed in the forward flow the stream of the synthesis gas taken from the first stage of the compressor, or from the intermediate stage and the stream of the liquid ammonia, essentially the dehydrated synthesis gas is separated from the mixture flow coming out of the mixer and guide it into the second stage of the compressor, which is located behind the first stage or behind the intermediate stage. The technical result of the invention consists in the rise of the conversion outlet and in the decrease of the power inputs.

EFFECT: the invention ensures the increased conversion outlet and the decreased power inputs.

10 cl, 2 dwg

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