Method for separation of waste gas or smoke produced in process of fuel oxidation, and extraction of carbon dioxide from it

FIELD: technological processes.

SUBSTANCE: invention may be used in chemical industry and environment protection. Waste gas flow is cooled, compressed by compressor and then passed through material that is half-permeable for gas, for instance, molecular sieve or activated coal. Adsorption and desorption of carbon dioxide in half-permeable material is carried out in compliance with adsorption technology at periodical change or swinging of temperature (AKT). Part of separated gas flow that contains highly concentrated carbon dioxide is used as initial material for production of ammonia and urea or methanol or is collected and stored for further use.

EFFECT: lower consumption of energy, reduced structural expenses and expenses on servicing.

5 cl, 1 dwg

 

The technical field to which the invention relates.

The present invention relates to a method for separation off-gas or smoke generated during the oxidation of the fuel, and excretion of carbon dioxide. The invention relates in particular to a method of carbon dioxide from exhaust gas or smoke from the air oxidation of fossil fuels or their fractions or derivatives, through its division.

The term "oxidation" in the context of the present invention is implicit and normal combustion, in particular fossil fired in the air in a domestic or industrial purposes, and electrochemical oxidation of the fuel occurring, for example, in fuel cells.

The level of technology

It is known that at present exhaust (flue) gases or smoke generated in the combustion process or in other processes of the natural oxidation (burn) of fuel in the domestic environment or in industrial plants, usually vented into the atmosphere, thereby creating serious problems associated with environmental pollution. The most serious problems associated with a global increase in the temperature of the planet, known as the "greenhouse effect", and is due primarily to the increase in the content in the Earth's atmosphere of carbon dioxide, which gets it together with rabotniki gases or smoke.

In addition, it is known that in certain industrial process carbon dioxide is used as the source of the product, including processes include, in particular, processes that use thermal energy obtained by burning fossil fuels. Obviously, in these cases, to increase productivity and/or reduce the cost of raw materials it is advisable to use carbon dioxide at least partially isolated from forming in the combustion process off-gases.

It is known, for example, that is used to produce ammonia and urea or methanol starting materials, such as hydrogen, carbon monoxide and carbon dioxide, are usually obtained in the form of a gaseous mixture in the reforming of methane or other light hydrocarbons such as natural gas, LPG (liquefied petroleum gas) and nafta.

The conversion of methane is carried out in a special oven, which is part of the whole installation reformer, usually intended to produce ammonia and urea or methanol, using the heat obtained by combustion with air in some part of the source of methane.

Upon receipt of the ammonia and urea for the conversion of hydrogen into ammonia to the resulting reforming gas mixture in stoichiometric proportions add nitrogen.

However, to icesto carbon dioxide contained in the resulting gaseous mixture is less than the stoichiometric amount required for conversion into urea just received of ammonia, which, obviously, reduces the performance of the equipment for production of urea.

And, conversely, upon receipt of the methanol, the amount of hydrogen contained in the received in the process of reforming a mixture of gases, sometimes exceeds the amount of hydrogen required for conversion to methanol entire monoxide and carbon dioxide, and therefore taken out of the synthesis reactor, the excess hydrogen is often used as fuel.

Obviously, performance and installation for obtaining urea and installation for the production of methanol can be significantly increased by allocating at least part of the carbon dioxide contained in the gaseous combustion products formed during the reforming of methane.

The problem with the separation and capture of carbon dioxide from the gaseous combustion products or smoke, is quite acute in recent decades has been the object of the most diverse and numerous studies. Most of these studies have been associated with the development of new ways to "wet" the separation of mixtures of gases and the separation from it of carbon dioxide. Offered on the basis of these research methods-wet cleaning of kazooba the different products of combustion were based on the use of appropriate solvents or solvent, able to selectively absorb carbon dioxide, followed by separation of carbon dioxide from solution or solvent by heating.

However, all currently known such methods have various disadvantages, which limit the possibility of their industrial applications.

One of the more significant disadvantages associated with the oxidation of the various components of the washing solution, which occurs under the action of oxygen contained in the gaseous products of combustion, and requires frequent replacement of the solution.

In addition, in the gaseous combustion products usually also contain sulfur and nitrogen oxides (SOxand NOx), which interact with some components of the washing solution and form stable salts and other undesirable compounds, it is difficult allocated from the solution and is recyclable.

The need for frequent replacement of the wash solution and removal and recycling of unwanted compounds produced during decomposition, respectively, increases the cost of the whole process of separation of the gaseous combustion products and the allocation of these carbon dioxide.

In addition, current equipment for the separation of gaseous combustion products and the selection of them dioxide of plastics technology : turning & the Yes is marked by a relatively high complexity, has a high cost, is time-consuming to maintain and takes up a lot of space and therefore require large investments and costs for routine maintenance.

The present invention was based on the task to develop an effective and reliable method of separating the waste gases formed during the oxidation of the fuel, and the selection of them is carbon dioxide, which would allow to reduce energy consumption, construction costs and maintenance costs.

Summary of the invention

The above problem is solved according to the invention with its proposed method of separation of the exhaust gases formed during the oxidation of the fuel, and the allocation of these carbon dioxide, in the exercise of which the flow of exhaust gas is passed through a semi-permeable to gas material, in this semi-permeable to the gas material from passing through it the waste gas stream to separate a gas stream containing highly concentrated carbon dioxide, and use at least part of the gas stream containing highly concentrated carbon dioxide as raw material in industrial plant and/or collected and stored for subsequent use, at least part of the flow gas containing highly concentrated carbon dioxide.

Polyproline the output for strip material can be selected from the group including membrane hollow fibers and materials that can adsorb predominantly carbon dioxide, such as molecular sieves.

As the membranes of the hollow fibers, you can use two types of membranes, some of which mainly pass carbon dioxide, and other mostly do not miss it.

To the "molecular sieve" refers to all conventional microporous materials that can adsorb predominantly carbon dioxide contained in the gaseous mixture including activated carbon. Depending on the specific method of adsorption and release of carbon dioxide, all such materials are separated by molecular sieve or activated carbon type AAA (in which adsorption occurs at periodic variation or fluctuation pressure) or type of ACT (in which adsorption occurs at periodic variation or temperature swing).

While adsorption on AAA-technology containing carbon dioxide gas mixture is passed through a molecular sieve under pressure, which accelerates the preferential adsorption of carbon dioxide in the micropores of the molecular sieve. Subsequent reduction of pressure occurs simultaneously desorption of carbon dioxide and other gaseous components, held together with him in the micropores of the molecular sieve, and regeneration molekulyarnoj the sieve.

When the preferential adsorption of carbon dioxide in the micropores of the molecular sieve in the ACT-technology containing carbon dioxide partial mixture of gases is passed through a molecular sieve at a temperature not exceeding 80°C. the Desorption of carbon dioxide and other gaseous components, held together with him in the micropores of the molecular sieve, and the regeneration of the molecular sieve in this case, during the subsequent rise in temperature, for example by means of steam.

In the proposed in the invention method, it is preferable to use at least a molecular sieve type ACT.

Using the proposed method, the molecular sieve type ACT eliminates the need for compression of large quantities of shared gas and allows to obtain carbon dioxide at relatively low energy cost.

In addition, for the regeneration of the molecular sieves of the type of ACT it is sufficient to pass through them in pairs or in another embodiment, the part containing highly concentrated carbon dioxide gas flow heated to a temperature of regeneration of molecular sieves.

Using the proposed method does not molecular sieves type ACT, and the membranes of the hollow fibers or molecular sieves of type AAA less preferred because of the much greater flow of energy necessary for compression treatment is atively exhaust gases.

In addition, the use of the membranes of the hollow fibers is associated with a high cost, even with a significant increase in process efficiency and the emissions of carbon dioxide from other gaseous components contained in the waste gaseous products of combustion.

In a preferred embodiment of the invention it is proposed a method of separating gases of combustion and separation from them of carbon dioxide, which as a semi-permeable to gas material use material that can adsorb predominantly carbon dioxide and highlight from the stream of exhaust gas, the gas stream containing highly concentrated carbon dioxide, and in which the flow of exhaust gas is passed through a semi-permeable to gas is a material that adsorbs at least a substantial part contained in the exhaust gas flow of carbon dioxide, to obtain the output stream of gas with a low content of carbon dioxide passed through a semi-permeable to gas, the material gas with a low content dioxide carbon released into atmosphere and desorbed from a semi-permeable to gas material, at least a substantial portion of the carbon dioxide to obtain a gas stream containing highly concentrated carbon dioxide.

More distinctive features and advantages of the STW proposed in the present invention, a method of extraction of carbon dioxide from the waste gaseous products of combustion are considered in the description below, the example illustrates, but do not limit the invention variants of its possible implementation with reference to the accompanying description of the drawing.

Brief description of drawing

Attached to the description of the drawing is a schematic diagram illustrating a possible implementation of the present invention in the method of separating the waste gaseous products of combustion and the allocation of these carbon dioxide.

The preferred embodiment of the invention

Marked as shown in the drawing the figure 1 position of the unit is a furnace, reactor or combustor of household or industrial installations, which together with air and burn the appropriate fuel, in particular natural fuel.

Marked on the diagram the position of the 2 block is a heat exchanger designed to cool the stream of hot flue gas produced during combustion of the fuel in unit 1.

In the exhaust gas contains mainly carbon dioxide, water vapor, oxygen and nitrogen, as well as a limited number of nitrogen and sulphur oxides (SOxand NOx).

The block indicated by the position 3, a compressor which compresses it to the required pressure stream is cooled in heat exchanger 2 of the exhaust gases. The presence of the compressor 3 is optional, but it should be used when you is the bookmark of carbon dioxide using molecular sieves type AAA or membranes of the hollow fibers, when the processing of the exhaust gas requires a mandatory compression.

When using molecular sieves type ACT need to use compressor 3 is eliminated and it can be replaced by a simple fan.

Position 4 marked block with a semi-permeable to gas material, in particular a membrane or molecular sieve, which separates out of the unit 2 or unit 3 flow of exhaust gas to obtain a gas flow containing highly concentrated carbon dioxide, as described in more detail below.

Position 5 marked another compressor, which compresses flowing out of the block 4, the gas stream containing highly concentrated carbon dioxide.

Part received in block 4 of the gas stream containing highly concentrated carbon dioxide, heat another heat exchanger, which is indicated in the diagram position 6.

Formed in the block 1 hot exhaust gases are fed into the heat exchanger 2 to line 7.

In the heat exchanger 2, the waste gas stream is cooled to a temperature in the range from 20 to 80°C.

The flow of the cooled gas leaves the heat exchanger 2 through the pipe 8. When used in block 4 as a semi-permeable to gas material of the membranes of the hollow fibers or molecular sieve type AAA emerging from th the exchanger through the pipeline 8 cold exhaust gas is first compressed in the compressor 3 to the absolute pressure in the range from 1 to 20 bar, and only then through the pipeline 9 is applied to the block 4.

In the case when the block 4 as a semi-permeable to gas material used molecular sieve type ACT, the need for compressor 3 is eliminated, and the flow of exhaust gases from the block 2 immediately served in the block 4.

In block 4 semi-permeable to gas the material is released from flowing through the pipeline 8 or 9 of the flow of exhaust gases from a gas stream containing highly concentrated carbon dioxide.

In unit 4, it is preferable to use a molecular sieve type ACT, which takes place mainly nitrogen and which at the same time mainly adsorbed a mixture of gaseous components containing oxygen, i.e. mainly carbon dioxide, water vapor and pure oxygen.

Pipeline, marked in item 10 of block 4 in it after processing the exhaust gases emit gas, which mainly contains nitrogen.

For desorption of carbon dioxide and other oxygen-containing compounds adsorbed in unit 4, for a time block connected to the block 4 line 8 or 9 and regenerate in unit 4 located therein membrane hollow fibers or molecular sieve.

When using a membrane of hollow fibers or molecular sieve type AAA regeneration membrane or molecular is about SITA carried out by reducing the pressure in unit 4 (decompression) and release from the membrane or molecular sieve of adsorbed carbon dioxide.

When using molecular sieve type ACT regeneration of the sieves carried out by the method described in more detail below.

The pipeline 11 from unit 4 enters obtained in the process of regeneration of the semi-permeable to gas of the material gas in which the concentration of carbon dioxide is greater than the exhaust gas in the pipe 8 or 9. In out of the unit 4 through the pipeline 11 gas concentration of other adsorbed gaseous components is also higher than in the exhaust gas in the pipe 8 or 9.

Taken from unit 4 gas containing highly concentrated carbon dioxide can be used as a starting material to the corresponding industrial setting, either directly or after further processing. In another embodiment, the gas can after its liquefaction stored in liquid form in the appropriate place and then use as needed.

Containing highly concentrated carbon dioxide gas can, for example, via the pipeline 11 to submit to the appropriate compressor 5 and after compression in the compressor to correct pressure immediately be used as source material connected to the compressor by a pipe 12 to the device for producing urea or methanol.

For full or partial purification of the current flowing through the pipeline 11 gas from such gotoblas the s components, as oxygen and oxides of nitrogen or sulfur (SOxand NOx), it can be skipped under certain conditions through one or more membranes or molecular sieves and/or process in any other system of separation.

Completely or partially purified from the above gaseous components of the gas pipeline 11 to serve in the compressor 5 and after compression to a certain pressure to use as source material for urea or methanol.

In this scheme, the part containing highly concentrated carbon dioxide gas from the pipe 11 through the pipeline 13 is heated in the block 6 and then through the pipeline 14 is returned back to the block 4, in which it is used for the regeneration of the molecular sieve type ACT.

In another embodiment, for the regeneration of such screens you can use water vapor with high temperature.

When regeneration occurs desorption of gaseous components such as carbon dioxide in the micropores of the molecular sieve type ACT, which increases the concentration of carbon dioxide in the gas stream in the pipe 11.

For the person skilled in the art it is obvious that taking into account the specific requirements can accordingly be improved offer in the invention method, while staying within the volume of the crust is asego of the invention, defined by the claims.

1. The method of separation of the exhaust gases formed during the oxidation of the fuel, and the allocation of these carbon dioxide, in the exercise of which the flow of exhaust gas is passed through a semi-permeable to gas material, which is a molecular sieve or activated carbon, and then separating the gas stream containing highly concentrated carbon dioxide, in which adsorption and desorption in a semi-permeable to gas, the material gas flow containing highly concentrated carbon dioxide, conduct technology adsorption at periodic variation or temperature swing (the ACT), and use at least part of the gas stream containing highly concentrated carbon dioxide as raw material industrial plant and/or collected and stored for later use at least part of the gas stream containing highly concentrated carbon dioxide.

2. The method according to claim 1, wherein for the separation of the exhaust gases and the allocation of these carbon dioxide as a semi-permeable to gas material use material that can adsorb predominantly carbon dioxide and highlight from the stream of exhaust gas, the gas stream containing highly concentrated carbon dioxide, and in which the flow okadama what about the gas is passed through a semi-permeable to gas material, which adsorbs at least a substantial part contained in the exhaust gas flow of carbon dioxide with receiving the gas stream with a low content of carbon dioxide passed through a semi-permeable to gas, the material gas with a low content of carbon dioxide released into atmosphere and of the semi-permeable to gas material is desorbed at least a substantial portion of the carbon dioxide to obtain a gas stream containing highly concentrated carbon dioxide.

3. The method according to claim 2, in which the desorption is conducted by passing through a semi-permeable to gas material flow of steam or by passing the gas stream containing highly concentrated carbon dioxide, heated to the regeneration temperature of a semi-permeable to gas material.

4. The method according to any of the preceding paragraphs in which the oxidizable fuel is a natural fuel.

5. The method according to any of the preceding paragraphs, in which highly concentrated carbon dioxide is used at the facility to produce ammonia and urea or methanol.



 

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