Synergistic method for the production of methanol (options)

 

(57) Abstract:

The invention relates to a combined synergistic method of production of methanol and the production of tertiary butyl esters of lower Akilov partial oxidation of heavy hydrocarbon fractions. Synergistic method for the production of methanol comprises the electrolysis of water to produce hydrogen and oxygen, providing feed stream of organic combustible fuel supply at least part of the oxygen together with the stoichiometric amount of organic fuel in a partial oxidation reactor for receiving exhaust gases, including carbon monoxide and hydrogen, the supply of stoichiometric amounts of carbon monoxide and hydrogen in the synthesis of methanol for methanol production. An advantage of the present invention is that the process can be an effective sponge for carbon dioxide, one of the main compounds in the exhaust (greenhouse) gases. 3 S. and 31 C.p. f-crystals, 11 ill.

The present invention relates to a combined synergistic method of production of methanol, which essentially reduced the allocation of exhaust gases and preferably it is insignificant. The invention of the oxidation of heavy hydrocarbon fractions, in which a reduced selection of exhaust gases or preferably it is insignificant.

Tertiary butyl esters of lower Akilov, such as methyl tert-butyl ether (MTBE) and/or ethyl tert-butyl ether (ETBE), can be added to gasoline as an oxygenate. Such esters are relatively non-volatile components, which can be used to increase the octane number of gasoline.

These esters can be produced from methanol. The conventional process for production of methanol is the conversion of water vapor. According to this process, methane reacts with steam at high temperatures and pressures. Traditionally as a source of methane is natural gas. According to this process less than 85% of natural gas is converted to methanol. The remainder of the natural gas used as fuel for the process. One of the drawbacks of the conversion process steam is that it uses valuable commercial product, namely natural gas, for the production of methanol. Another disadvantage of converting steam is the fact that as a result of this process releases a significant amount of exhaust gases.

An alternative method produced the emer, natural gas is subjected to partial oxidation with pure oxygen with production of carbon monoxide (CO) and hydrogen. Oxygen is obtained from the cryogenic installation. Then the carbon monoxide and oxygen are served in the stoichiometric ratio in the synthesis of methanol.

As an additional alternative feedstock for the partial oxidation process can be used heavy destinationnode oil with a low number with obtaining oil with a higher number. The molar ratio of carbon monoxide and hydrogen in the produced raw materials for the synthesizer is equal to one to four to influence the synthesis of methanol. Accordingly, a mixture of carbon monoxide and hydrogen is exposed to the process of moving water, which converts about half of the monoxide of carbon, i.e. carbon from the oil feedstock and carbon from the cryogenic separation, carbon dioxide. Then, the carbon dioxide must be separated from the raw stream, which requires extensive and expensive capital equipment and subsequent maintenance costs. Then carbon monoxide and hydrogen in approximately stoichiometric proportions are fed into the reactor for methanol production. One of the drawbacks of this time. An additional disadvantage of this process is that the reaction of the movement of water required to obtain a stoichiometric quantities of carbon monoxide and hydrogen to methanol synthesizer. In addition, in this process, in essence, half of the monoxide of carbon, i.e. carbon and oxygen are converted to carbon dioxide, which does not contribute further to this process. High levels of carbon dioxide, flue gas (greenhouse gas) creates a negative effect on the environment aspect of the use of methanol fuels and has a very substantial loss of energy used. Accordingly, the use of oils with low octane, available in abundance, cannot be compared in value with the use of natural gas with a high octane number.

Brief description of the invention

According to the present invention created a synergistic method for the production of methanol comprising the steps:

a) electrolysis of water to produce hydrogen and oxygen;

b) providing a supply current to the organic combustible fuel;

C) feeding at least part of the oxygen obtained in stage a), together with the stoichiometric quantity mentioned organic the and and hydrogen;

g) feeding at least part of said carbon monoxide and hydrogen in the synthesis of methanol for the production of methanol; and

d) adding additional hydrogen in the synthesis of methanol to provide the stoichiometric supply of hydrogen and carbon monoxide mentioned methanol synthesizer.

According to an additional variant of the present invention the method includes the following steps:

a) electrolysis of water to produce hydrogen and oxygen;

b) providing a supply current to the organic combustible fuel;

C) feeding at least part of the oxygen obtained in stage a), together with the stoichiometric quantity mentioned organic combustible fuel in a partial oxidation reactor for receiving exhaust gases containing carbon monoxide and hydrogen;

d) ensuring the supply of raw stream of carbon dioxide for cooling the above-mentioned partial oxidation reactor in order to increase the temperature of said carbon dioxide to a temperature above the temperature of dissociation of said carbon dioxide;

d) supply mentioned heated carbon dioxide in said reactor for partial oxidation;

e) feeding on the edge of the g) adding additional hydrogen in the synthesis of methanol to obtain stoichiometric loading of hydrogen and carbon monoxide in the synthesis of methanol.

In an additional alternative embodiment, the methanol can be connected with isobutyl alcohol to obtain tert-butyl ether.

In an additional optional embodiment, the method may also include isobutylene synthesizer, in which Bhutan and pairs connected with obtaining isobutylene and hydrogen.

One of the advantages of the present invention is the use of electrolysis to obtain pure oxygen and pure hydrogen. Electrolysis unit can operate using the excess energy from energoproizvodyaschih companies. Traditionally energomontaj companies reduce the consumption of electricity in the evenings and on weekends. However, from the point of view of profitability, it is preferable to support the work of generating plants on a regular basis. Accordingly, it is possible to obtain a significant amount of excess energy at very low prices. The excess energy can be used for the production of hydrogen and oxygen is very high purity. Hydrogen and oxygen can accumulate for use when they may be required in the production of carbon monoxide.

An additional advantage of this method is that the use of electret be used to obtain a stoichiometric balance of carbon monoxide and hydrogen, fed to the methanol synthesizer.

The hydrogen for the synthesis of methanol can be obtained from the reaction of partial oxidation, and as a by-product of the manufacture of isobutylene. In this embodiment, the hydrogen from electrolysis units may be assembled and sold as a commercial product.

The method is particularly well adapted for the use of heavy hydrocarbon fractions such as gas oil or distillation residues from the cracking of crude oil. The method has many sources of hydrogen, such as, for example, from the production of isobutene or of the partial oxidation reactor, which can be used to obtain a stoichiometric amount of hydrogen to be added to the methanol synthesizer without the use of high-quality hydrogen produced by electrolysis installation, or without implementation of the displacement response of the water.

The method may also include an ethanol fermenter. For the production of methanol in ethanol fermenter can be added to the precursor alcohol and couples. Ethanol can be converted, using isobutylene with getting ETBE and additional quantities of hydrogen that is used to increase the production of methanol.

According to an additional alternative in the process can be included degeneria installation. In agenerase installation part of the hydrocarbon recycled raw materials can be burned to produce steam, electricity and exhaust gases. Electricity can be used to supply electricity to the electrolysis units. Pairs can be used in various locations throughout the process, as, for example, to compress gas, discharge liquid, the steps of heating in the process, as, for example, in fermentation, distillation and other. Exhaust gases can be used to provide the source of the CI can also be used to create effective joint production process MTBE and ETBE, at the same time significantly reducing or eliminating the allocation of waste (greenhouse) gases.

In an additional alternative embodiment of this method the carbon dioxide from the vent gases or atmosphere can be skipped through the heat exchanger, which is attached to the partial oxidation reactor. The carbon dioxide must be heated reaction products of the partial oxidation reactor to a temperature within or above the dissociation of carbon dioxide. Once the carbon dioxide is heated to this temperature, it dissociates with the formation of carbon monoxide, which can then be fed into the synthesizer of methanol, and oxygen, which can be fed to the partial oxidation reactor.

Brief description of drawings

These and other advantages of the present invention become clearer from the following description and the attached drawings of a preferred variant of the method which is the subject of the invention, where:

Fig. 1 is a flow chart of the process of one embodiment of the present invention;

Fig. 2 is a diagram of a second variant of this process, demonstrating the use of plants for the production of gas for proceduremay process of the third variant of the present invention, depicting the production of ethanol;

Fig. 4 is a variation of the circuit of Fig. 3;

Fig. 5 is a diagram of an alternative process for the partial oxidation reactor;

Fig. 6 is a schematic process diagram of a process for electrolysis, as shown in Fig. 1, 2, 3, and 4;

Fig. 7 is a process diagram that includes sagterious the installation of combined cycle;

Fig. 8 is a process diagram of the process, including sagterious installation with a single loop;

Fig. 9 is a variation of the circuit of Fig. 2;

Fig. 10 is a diagram of an alternative process of the present invention; and

Fig. 11 is a diagram of an additional alternative process of the present invention.

Description of the preferred option

As shown in Fig. 1, according to a preferred variant of the present invention process involves the electrolysis unit 10, a partial oxidation reactor 12, gazoochistnoe installation 14 and the methanol synthesizer 16. The process may also include a synthesizer ether 18 for the production of tertiary butyl esters of lower alkyl, and isobutylene synthesizer 20.

Electrolysis unit 10 and esto is supplied to the electrolysis unit by means of conduit 22. In electrolysis cells subjected to the electrolysis of water usually flows in a constant stream. Accordingly, the electricity supplied to the electrolysis unit 10, is fed to the rectifier DC power supply (not shown) to obtain a constant electric current, which is then used in the electrolysis cell electrolysis units 10. Water, as, for example, in the form of condensate, boiler feed water, and the electrolyte, such as sodium hydroxide (caustic soda), served through the process streams 24 and 26, respectively, in the electrolysis unit 10. As shown in Fig. 6, electrolysis unit 10 can contain multiple electrolysis cells 28 that are used to electrolyze water into hydrogen and oxygen. Hydrogen and oxygen are separated using known means and can be transported in containers or receptacles 30 and 32, respectively. Then the hydrogen and oxygen can be compressed by the compressor 34 and 36, respectively. Compressed oxygen can then accumulate in the collection vessel 38. Similarly compressed hydrogen may accumulate or be stored in the accumulation of hydrogen vessel 40. Cumulative receptacles 38 and 40 provide tanks of oxygen and hydrogen that can be used when not udaetsya in cumulative vessel 38 via a supply flow 37. If the electrolysis cell 28 receive heavy water, the latter is served in the cumulative suitable receptacle (not shown) through the process stream 46.

Electrolysis is a very energy intensive process. According to the present process, the electricity used in the electrolysis unit 10 is excess electricity that can be obtained during off-peak hours at a very low price from energy corporations. Alternatively, as will be discussed below, agenerase reactor can operate on a permanent basis for the production of process steam used in industry. However, the demand for electricity can be reduced at night or weekends. In these off-peak hours electricity can be unclaimed and can be used for electrolysis cells 28. Similarly, various forms of energy are usually served in several generating stations during the day to supply electricity to various companies and industries. In the evenings and weekends industrial enterprises slow down or stop working and, therefore, consume less electricity. However, the generating equipment can be maintained in the working status is the sing in the process according to the present invention. Accordingly, according to the present process electrolysis unit can be used to convert excess energy into stored chemical energy (namely, in the form of oxygen and hydrogen). Accumulated chemical energy can then become available for use at a convenient time equipment that works in the process according to the present invention.

The partial oxidation reactor 12 includes a partial oxidation reactor to convert source of hydrocarbons, essentially carbon monoxide and hydrogen. Other gases partial oxidation may include small amounts of steam, carbon dioxide and hydrogen sulfide. What gases are produced in the partial oxidation reactor depends, in particular, from which hydrocarbons are recycled to the reactor. Preferably the hydrocarbon feedstock used in the present process, is a product with a relatively low number and preferably includes a heavy oil such as gas oil which has a boiling point higher than about 650oF (343,33oC) or distillation residues (which have a boiling point of about 1000oF (537,78oC) processing Neth. 1, the oil can be delivered through the pipe 50 in the accumulator tank 52. Oil is transported from the storage tank 52 through the process stream 54 in the partial oxidation reactor 12. Oxygen is supplied through the process stream 44 from electrolysis units 10 in the partial oxidation reactor 12. Preferably, the partial oxidation reactor 12 uses non-catalytic partial oxidation process in which a hydrocarbon feedstock reacts at high temperature and usually high pressure with oxygen, oxygen-enriched air or air. Preferably, as shown in Fig. 1, the oxygen from the electrolysis units 10 are used in the partial oxidation reactor 12. In the process, produces mainly carbon monoxide with a small amount of carbon dioxide, steam, and if the raw material contains sulfur, hydrogen sulfide. The process effectively uses raw materials without producing heavy hydrocarbons, tar and other potentially problematic by-products, such as oxides of sulfur or nitrogen.

Typically, the partial oxidation reactor operates at a temperature of from about 1200oC to about 1500oC. the Working pressure is usually sostavlenie feedstock is converted in the exhaust gases. The gas leaving the partial oxidation reactor can be cooled by contact with water in the quenching chamber or can be used to power a steam boiler by indirect heat exchanger (not shown). Alternatively, as will be discussed hereinafter, the gas can be cooled by the incoming stream of carbon dioxide.

The advantage of the partial oxidation reactor is that part of the carbon fuel not used to generate heat for the process. This is comparable to the conversion of methane by steam, in which about 15% or more of the processed natural gas is consumed to provide process energy. Another advantage of this process is that due to the highly reducing atmosphere in the reactor are not formed allocation of nitrogen oxides, sulfur oxides, or carbon dioxide. The partial oxidation reactor 12 operates on the basis of zero emission, i.e. emission or release of harmful waste (greenhouse) gases, essentially, is not significant.

Exhaust gases from the partial oxidation reactor are transported through the process stream 56 in the gas cleaning plant 14. The gas cleaning plant 14 processes the exhaust gases on the oxidation may form hydrogen sulfide. The hydrogen sulfide can poison the catalyst used in the methanol synthesizer 16. Accordingly, harmful amounts of hydrogen sulphide must be removed. The hydrogen sulfide can be removed through the use of process-based amination, for example, one that uses MDEA. Also can be removed and other by-products, such as steam or oxides of traces of elemental metals.

Fume treatment unit 14 produces, essentially, a clean pair of carbon monoxide and hydrogen 70. If the quality of the processed material used heavy oil, the ratio of carbon monoxide to hydrogen in the exhaust gas is approximately 1:1 (i.e. 2 of the hydrogen atom on each carbon atom). Methanol contains 4 atoms of hydrogen per atom of carbon. Accordingly, additional compensating hydrogen must be supplied in such a way that the methanol synthesizer 16 it was possible to submit the stoichiometric amount of carbon monoxide and hydrogen.

The methanol synthesizer 16 converts carbon monoxide and hydrogen in methanol. Carbon monoxide and hydrogen are fed into the synthesizer of methanol through the process stream 70, and optional hydrogen may PY stream 74 is used to ensure that in the methanol synthesizer 16 is essentially stoichiometric amount of hydrogen and carbon monoxide. As mentioned above, depending on the processed material additional hydrogen may be necessary to provide at least about stoichiometric amount of carbon monoxide and hydrogen. Methanol can be stored in a storage tank (not shown) or sold as a commodity on the market. Alternative, some or all of the methanol can go through the process stream 76 into the synthesizer simple ether 18. The flow of carbon monoxide and hydrogen in methanol synthesizer 16 preferably has a stoichiometric proportion. Accordingly, the molar ratio of carbon monoxide and hydrogen gas preferably is about 1:2 (i.e., four atoms of hydrogen per atom of carbon).

Hydrogen for methanol synthesizer 16 may be obtained from the accumulation tank of hydrogen. The reservoir may contain hydrogen derived from electrolysis units 10 and/or isobutilene synthesizer 20 and/or any available source. You must understand, if for partial oxidation reactor COI is about half the number of hydrogen required for methanol synthesizer 16. Accordingly, the additional hydrogen from electrolysis units can be used in addition to hydrogen from gas treatment system 14. Alternatively, if the equipment includes isobutilene synthesizer 20, the hydrogen produced in isobutilene synthesizer 20 may be used for additional supply of hydrogen methanol synthesizer 16.

The methanol from the methanol synthesizer 16 is fed through the process stream 76 into the synthesizer simple ether 18. As can be seen from Fig. 1, steam, water and isobutylene are served through process streams 78, 80 and 82, respectively, in the synthesizer 18. The synthesizer 18 converts isobutylene, steam, methanol and water in MTBE, heat and waste water indicated by process flows 84, 86 and 88, respectively. As shown in Fig. 1 by the dashed line in the synthesizer 18 can be fed ethanol to obtain as ETBE and MTBE. One of the special advantages of this process is the production of ETBE. ETBE more effective as an oxygenate and magnifier octane number. However, these advantages are currently excluded due to the high cost of production of ETBE. However, ETBE can be done better and cheaper by filing e is / establishment, which number or all of the methanol 76 may be stored or sold as a commodity on the market.

MTBE can be transported via pipeline to storage tank, where it can essentially be used in the plant or sold as a commodity on the market. Isobutylene for the synthesizer 18 may be obtained in the form of goods from the market. Alternatively, as shown in Fig. 1, isobutylene can be obtained from the isomerization/isobutilene synthesizer 20. Process steam and butane are served through process streams 90 and 92, respectively, in isobutilene synthesizer to produce isobutilene stream 82.

In General, the process shown in Fig. 1, is a synergistic process for the production of MTBE. The process is advantageous because as a result of its implementation in the environment are not outgoing (greenhouse) gases. The process uses the excess energy and petrochemical products with low octane for the production of MTBE is more cheap and non-polluting way.

Potential sources of hydrogen for methanol synthesizer 16 in more detail is shown in Fig. 2. As can be seen from Fig. 2, the hydrogen can be obtained from electrolysis units 10 (process stream 42) and/or from isobutilene synthesizer 20 (process stream 94). Hydrogen from biologicheskii stream 76) may be submitted to the Central hydrogen storage (e.g., accumulating tank 40 shown in Fig. 6). Then the required amount of hydrogen can be fed to the methanol synthesizer 16. However, the hydrogen from each of these sources has a different purity. Each of them can be stored separately for later use in the process or for sale as a commodity on the market. For example, as shown in Fig. 2, the hydrogen from isobutilene synthesizer 20 and electrolysis units 10 can be stored separately and be submitted when required in the methanol synthesizer 16. Accordingly, hydrogen from electrolysis units 10 can be fed through the process stream 41 in the hydrogen storage 40. Hydrogen from isobutilene synthesizer 20 is supplied process stream 94 in the methanol synthesizer 16. Excess hydrogen can be removed from the process stream 94 cumulative equipment via a process stream 96 for later use or sale. Accordingly, the synthesizer methanol can be powered by hydrogen from electrolysis units 10 and/or isobutilene synthesizer 20.

In an alternative preferred embodiment, the reactor for the production of gas 100 converts carbon dioxide to carbon monoxide by dissess, the carbon dioxide fed into the reactor for the production of gas 100 flows through 102 and 104. Preferably, carbon dioxide was at atmospheric pressure. Steam is supplied into the reactor for the production of gas 100 through the process stream 106. The steam is used for heating layer in the reactor, and through this heated layer or above it miss dioxide. Passing over the heated layer, the carbon dioxide is heated to a temperature higher than the temperature of dissociation of carbon dioxide (approximately 1100oC at 1 ATM) Discharge vapor is removed from the reactor via stream 108. Carbon monoxide from the reactor for the production of gas 100 is used to replenish the carbon monoxide from the partial oxidation reactor 12. This increase in the number of processing raw material in the methanol synthesizer 16 may be used to increase the yield of methanol from the methanol synthesizer 16. Increase the amount of carbon monoxide in methanol synthesizer 16 also requires the input of additional hydrogen. As mentioned above, hydrogen can be obtained by issuing a certain amount of hydrogen, which otherwise may be sold as a by-product of the process. Preferably,isobutilene synthesizer 20.

Carbon dioxide to the reactor for the production of gas 100 may come from other processes within the system. An example of such processes is an ethanol fermenter 120. Ethanol fermenter 120 produces ethanol, which is represented as the process stream 122 in Fig. 2. A byproduct of fermenters 120 is carbon dioxide, which can be served through the process stream 102 into the reactor for the production of gas 100. Alternatively, the carbon dioxide from an alternative source, for example, purchased on the market, may also be served through the process stream 104 into the reactor for the production of gas 100.

One of the advantages of adding an ethanol fermenter 120 is the expansion of simple synth ether 18 to production as ETBE and MTBE. Accordingly, the synthesizer simple ether 18 may include, in addition to the methanol reformer, ethanol reformer for the production of ETBE (process stream 124).

Additional alternative preferred variant shown in Fig. 3. This option is a modification of the variant shown in Fig. 2. In particular, a variant demonstrates the process of using municipal solid kautsa via a supply flow 130 in the separation unit municipal solid waste 132. In addition, other natural sources of cellulose solid waste such as corn cobs cobs, Newspapers, cereal dry food and wood waste can be submitted through the process stream 134 in the separation unit municipal solid waste 132. Air and electricity are also available in the installation 132 flows through 136 and 138, respectively. Waste're segregated in the installation of 132 in different groups. They can include metals, organics, wood waste, plastic, cellulose, and other less valuable products. Recoverable metals can be sent via process stream 140 to the pusher and disposal 142. Product installation 142 can be sold as metal scrap for use in operations recirculatory. Organic material such as kitchen and garden waste can be sent through the process stream 144 in the installation of formation of products fertilizers 146. The extracted wood waste can go through the process stream 148 in the installation of the formation of fibreboard 150. Retrieved plastic can go through the process stream 152 in the installation reformer plastic 154. Cellulose is and the preparation of cellulose 158 may use burovzryvnye processes, for example, such as that provided by Stake Technology Ltd. for the production of cellulose for ethanol fermenter 120. Accordingly, electricity and high-pressure steam is served by process streams 160 and 162 in the installation preparation of cellulose 158. Installing 158 produces purified cellulose (process stream 164), waste heat and waste water (process flows 166 and 168, respectively). Other low-value products and materials may be sent through the process stream 170 in the accumulation or storage equipment, from which they can be transported to the place of burial in the earth.

Purified cellulose, cobs of corn, grain and other feed materials may be sent through workflows 164, 172 and 174, respectively, in ethanol fermenter. Steam and electricity are also served through the process streams 176 and 178 in an ethanol fermenter 120. Ethanol fermenter 120 produces waste heat (process flow 180), waste water (process stream 182) and dried grains (process stream 184).

As can be seen from Fig. 3, the process is also adapted for inclusion in sagterious installation, the process may be included in sagterious installation 200. Hydrocarbon and air are burned in agenerase installation for the production of steam, electricity and exhaust gases. Hydrocarbons may be the same or different from that served in the partial oxidation reactor. As can be seen from Fig. 3, uses the same source of hydrocarbons and, accordingly, in sagterious installation 200 through the process stream 54 is fed heavy oil. Air is supplied to sagterious installation through the process stream 202. Water is also served in sagterious installation through the process stream 204. Degeneria unit produces pairs 206, electricity 208 and exhaust gases 210.

Degeneria installation can use either one reactor cycle, or reactor combined cycle. Typical agenerase process combined cycle using a turbine internal combustion shown in Fig. 7, and a typical agenerase process with one cycle that uses steam turbine shown in Fig. 8.

According Fig. 7 agenerase process combined cycle turbine uses internal combustion 220. Fuel 54 and the air/oxygen 202 are served in the turbine internally which I passed to the generator 224 through the power outlet 226. The rotation of the turbine is transmitted through the power outlet 226, causing the generator 224 to generate electricity 208. Flue gas 222 of the combustion turbine 220 is fed into the heating boiler 228. Heating boiler 228 effectively operates as a heat exchanger, which transfers heat from the flue gas to the water in the boiler 228. Flue gases, achladies, are drawn from the boiler 228 as exhaust gases. The heat transfer from the flue gases 222 in the boiler produces steam 230. Pairs 230 is fed to the steam turbine 232. When couples 230 passes through a steam turbine 232, the steam causes the turbine to rotate. This rotation is transmitted to the generator 236 through the power outlet 234 and causes the generator 236 to produce electricity 208. When the steam passes through a steam turbine 232, a portion of the steam condenses and the condensate returns to the boiler 228 through return flow 238. The rest of the steam, which is at lower temperature and pressure than steam 230, can be used as process steam in industry or at alternative stages discussed above. Process steam is fed in the rest of the industry through the supply flow 206. Steam, which is used in order narapidana water (not shown).

During normal operation of the turbine internal combustion nitrogen, inert gas, is drawn into the turbine in combination with an oxygen component of the supplied combustion air. This inert gas carries out two functions. The heated inert gas by burning fuel causes it to expand and, consequently, increases its pressure. The inert gas leaves the turbine, causing rotation of the blades and the shaft, which helps the products of combustion to produce energy. The inert gas also reduces the temperature of the combustion products to prevent damage metallurgy and materials of construction of the turbine 220 due to excessively high temperatures. These turbines internal combustion suggests that the use of nitrogen as the inert gas creates unacceptably high levels of nitrogen oxides, nitric oxide (NO) and nitrous oxide (N2O), which combine with atmospheric moisture to form components of acid rain. It is therefore desirable to replace the nitrogen with an inert gas that does not contribute to acid rain.

In the process of the present invention shown in Fig. 7, the exhaust gas 210 contains mostly carbon dioxide, purified in the gas purifying installation 320, and the purified exhaust gas is on and the air from flowing into the turbine flow. The oxygen required for combustion of the fuel can flow at least partially from the electrolyzer 330, which may be a component of electrolysis units 10 in the other figures of this description, or may be an independent installation. Electrolysis tank 330 is similar to cell 10, shown above. Oxygen can be provided by the stream 334 entering combustion turbine, to form at least part of the oxygen combustion 202. The hydrogen produced in the electrolysis installation 330 can be fed via stream 332 for mixing with the fuel 54 to form at least part (hythane) 336 to provide an improved fuel for the combustion turbine. Alternative, some or all of the oxygen required for the combustion of fuel can be achieved, at least partially, from an air separation unit 340. The oxygen obtained from the air separation unit 340 can be fed stream 342 to the input of combustion turbine. Nitrogen and other inert gases are transported by streams 334 store nitrogen 350 or for commercial sale.

Accordingly, the carbon dioxide circulating through the turbine internal SG is the flow of carbon dioxide 324 have a high concentration, essentially pure carbon dioxide. Accordingly, part of the carbon dioxide can be allocated to the stream 325 for feed to the reactor for the production of gas with the formation of at least part of the feed stream 102, and/or for submission to the partial oxidation reactor to form at least part of the feed stream 300, and/or for submission to the repository, and/or for commercial sale. Accordingly, the concentrated carbon dioxide can be obtained without using chemical equipment absorption separation, as required in the conventional system of internal combustion "in one pass".

According Fig. 8, agenerase process with one cycle uses steam boiler 250. Fuel 54 and air/oxygen stream 202 is served in a steam boiler 250. Fuel combustion in the boiler 250 produces flue gases 210 and couples 252. Pairs 252 is supplied to the steam turbine 254. When couples 252 passes through a steam turbine 254, it causes the turbine to rotate. This rotation is transmitted to the generator 260 via power outlet 256. Rotation of the power outlet 256 causes the generator 260 to generate electricity 208. When couples 252 passes through a steam turbine 254, part of the steam condenses and the condensate of vozvrashaet is 2, can be used as process steam in industry or in the alternative stages discussed above. Process steam is fed in the rest of the industry via stream 206. Steam used for heating purposes in the plant, is recycled into the steam boiler 250 through the circulating stream 262. Optionally, steam boiler 250 is added to the makeup water.

Agenerase reactor can be consumed by the industry, which uses steam and electricity for industry. Accordingly, process steam 206 can be used in industry for heating or other purposes, if necessary. Similarly, electricity 208 can be used in industry or transmitted in energy network (not shown) for sale to other consumers of electricity when you need it. Alternatively, part of the electricity can be used electrolysis unit 10 to electrolyze water to produce hydrogen and oxygen, as discussed above.

This flue gas stream 210 is cleaned in a gas cleaning installation 320 and returned to the process stream 324 to enter into the turbine combustion. When normal operate ozdoba burning. Inert gas is used to reduce the temperature of products of combustion in the boiler to prevent damage to the metallurgy and materials of construction of the boiler due to excessively high temperatures. The operation of these conventional steam boilers suggests that the use of nitrogen as the inert gas creates unacceptably high levels of nitrogen oxides, nitric oxide (NO) and nitrous oxide (N2O), which combines with atmospheric moisture to produce the components of acid rain. It is therefore desirable to replace the nitrogen with an inert gas that does not contribute to acid rain.

In the variant shown in Fig. 8, the inert gas is carbon dioxide, which is a major component of the off-gas flow 210 is purified in the gas purifying installation 320 and returns through the process stream 324 to the input of the boiler 250. This procedure eliminates the input of nitrogen and air from the boiler furnace. The oxygen required for combustion of the fuel can flow, at least partially, from the installation of water electrolysis 330, which may be a component of electrolysis units 10 shown in other figures of the present description, or may be an independent installation. Electrolysis unit 330 loads the practical stream 334 to the input of the boiler 250 to form at least part of the oxygen combustion 202. Hydrogen produced by electrolysis installation 330, may be supplied through process stream 332 for mixing with the fuel 54 to form at least part of the fuel mixture 336 to supply improved fuel steam boiler 250. Alternatively, the oxygen required for combustion of the fuel can flow, at least partially, from an air separation unit 340. Oxygen from the air separation unit 340 can be served through the process stream 342 to the input of the boiler 250. Nitrogen and other inert gases are transported through the process stream 344 store nitrogen or for commercial sale. Accordingly, the carbon dioxide circulating through the steam boiler 250, the off-gas flow 210, fume treatment unit 320 and the process stream of carbon dioxide 324 become highly concentrated to essentially pure carbon dioxide. Accordingly, part of the carbon dioxide may be introduced into the process stream 325 for feed to the reactor for the production of gas forming at least part of the feed stream 102, and/or for submission to the partial oxidation reactor, forming at least part of the feed stream 300, and/or feed in storage is the use of chemical equipment or equipment adsorption separation, as is required in conventional systems combustion "in one pass".

In alternative embodiments, Fig. 3, 4 and 10 degeneria installation 200 produces exhaust gases 210, mainly containing carbon dioxide, water vapor, nitrogen and oxygen. In addition, in the exhaust gas 210 also has a small amount of sulfur and nitrogen oxides. Exhaust gases 210 is cleared in the installation of flue gas cleaning 270 through this way to produce a gas stream containing essentially oxygen and nitrogen (flow 272) and a gaseous stream of water vapor, and CO2H2, SO2and SO3(stream 274). The gas flow 272 can be safely released into the atmosphere through an exhaust pipe 276. The gas stream 274 is fed into the installation deformirovaniya carbon dioxide 278. Installation 278 stream 274 is processed to carbon dioxide. This results in the wastewater stream 280, which may be disposed of or sent for additional processing, and gas flow 282, which essentially contains carbon dioxide. The carbon dioxide can accumulate and sold as a commodity on the market or used as raw materials for the installation for the production of gas 100 and/or partial oxidation reactor 12.

Accordingly, together with the installation of flue gas 270 the whole process preserves the zero discharge or emissions in the production of methanol.

In Fig. 4 shows an additional alternative. In this embodiment, the hydrogen from the gas treatment system 14, the hydrogen from electrolysis units 10 and hydrogen from isobutilene synthesizer 20 (namely, the process flow 72, 42 and 94, respectively) are served in the Central reservoir, where the hydrogen is combined for use, when it might be needed in the synthesis of methanol, or for sale on the market. In addition, as mentioned above, due to the different quality of the process streams 72, 42 and 94, hydrogen can be combined in one Central storage tank or many storage containers to save separately for each separate stream of hydrogen.

As should be clear from the above, the rate of methanol production depends on the rate of supply of carbon monoxide. To power the hydrogen of methanol synthesizer 16 available in various sources. The partial oxidation reactor may be the only source in oboudi fermenter 120, degeneria installation 200 and reactor for the production of gas 100 may also be included in the equipment. Degeneria installation and ethanol fermenter both are sources of carbon dioxide. The reactor for the production of gas 100 converts carbon dioxide from any of these sources or, alternatively, the carbon dioxide, which is purchased on the market in carbon monoxide. Accordingly, the reactor for the production of gas 100 may be a weak point in the rate of production of methanol and, consequently, MTBE and/or ETBE.

According to the present invention also describes an improved partial oxidation reactor 12. In accordance with this improvement support additional carbon monoxide is produced by the reactor for the production of gas 100 is reduced, and in some cases, the reactor for the production of gas 100 may not be required.

According Fig. 5, the oxygen supplied to the partial oxidation reactor 12 via stream 44. Hydrocarbon raw materials processed is fed to the partial oxidation reactor 12 through the process stream 54. The partial oxidation reactor 12 produces a gas stream 56. In accordance with the improvement of the reactor custom stream 304. The carbon dioxide may be obtained from an ethanol fermenter 120, agenerase installation 200 or purchased on the market. In the cooling casing 302 dioxide is heated to a high temperature. The heated carbon dioxide invention is fed via stream 306 in the heat exchanger by indirect heat exchange 308. The gas flow 56 is also fed to the heat exchanger. In the process of passing through the heat exchanger 308, the flow of carbon dioxide is additionally heated, and the gas flow 56 is cooled. Through this process, the carbon dioxide is heated to a temperature within or above the dissociation of carbon dioxide (above 1100oC, preferably above 1250oC). At this temperature the carbon dioxide dissociates with the formation of carbon monoxide and oxygen. Stream 308 is then supplied to the partial oxidation reactor 12. Through this process, the carbon dioxide from internal or external source is converted into carbon monoxide and oxygen, using available waste heat in the partial oxidation reactor. Accordingly, for the production of an increased amount of Molokai carbon does not require additional hydrocarbon raw materials processed.

In Fig. 9 shows an example of this is the use of the partial oxidation reactor of Fig. 5 to convert carbon dioxide to carbon monoxide with the exception of the use of the reactor for the production of gas. However, in this embodiment, the carbon dioxide obtained in the ethanol reactor 120, served through process flow 300 in the cooling casing 302 and is introduced into the cooling shroud in the form of a process stream 304. As should be clear, ethanol reactor 120 may be only one of many possible sources of carbon dioxide for cooling the casing 302.

Fig. 10 is another example of this later option. A variant of this figure differs from the variant of Fig. 3 the use of the partial oxidation reactor of Fig. 5 and 9 for converting carbon dioxide to carbon monoxide in addition to or alternative with the exception of the use of the reactor for the production of gas.

In Fig. 11 shows an additional alternative preferred option, such option, shown in Fig. 2. In this case, all of the carbon monoxide to methanol synthesizer 16 is obtained from a reactor for the production of gas. Accordingly, the partial oxidation reactor 12 and fume treatment unit 14 is not required.

Accordingly, an advantage of the major joints of the exhaust (greenhouse) gases. By modifying the partial oxidation reactor, is shown in Fig. 5, or exceptions reactor for the production of gas 100 carbon dioxide is converted into carbon monoxide, which is then transported into the synthesizer methanol for methanol production. The methanol is then converted to obtaining MTBE. Thus, flue or exhaust (greenhouse) gas is efficiently converted to MTBE, which can be used as an oxygenate for oxygen saturation of gasoline to improve combustion.

Example 1

In electrolysis installation gave 100 MW of electricity. Electrolysis unit 10 used the electricity for the production of 3800 lb/h (1723,68 kg/h) of hydrogen, 85 lb/h (38,556 kg/h) heavy water and 29860 lb/h (13544,5 kg/h) oxygen. Oxygen together with 26330 lb/h (11943,3 kg/h) gas or oil No. 6 was submitted in the partial oxidation reactor 12. The partial oxidation reactor 12 produces 56160 lb/h (25474,2 kg/h) exhaust gases, which come in gazoochistnoe installation 14. Fume treatment unit 14 produced 3513 lb/h (1593,5 kg/h) of hydrogen and 52253 lb/h (23701,96 kg/HR) carbon monoxide. Carbon monoxide together with 7465 lb/h (3386,12 kg/h) of hydrogen fed into the methanol synthesizer 16. The methanol synthesizer integator filed 108237 lb/h (499096,3 kg/h) of Bhutan. Isobutilene synthesizer produced 3732 lb/h (1692,84 kg/h) of hydrogen and 104505 lb/h (47404,5 kg/h) of isobutylene. Isobutylene was filed in the simple synth ester 18 with methanol. The simple synth ester produced 164222 lb/h (74491,1 kg/h) MTBE.

Example 2

Example 2 demonstrates the equipment depicted in Fig. 4, which is designed for the production of 380 million gallons per year of methanol. In the electrolysis unit 10 was applied for 100 MW of electricity for the production of 3800 lb/h (1723,68 kg/h of hydrogen, 85 lb/h (38,556 kg/h) heavy water and 30400 lb/h (13789,44 kg/h) oxygen. 26330 lb/h (11943 kg/h) gas or oil No. 6 and 29860 lb/h (13544,5 kg/h) oxygen was submitted in the partial oxidation reactor. The resulting gases were enrolled in gazoochistnoe installation 14, which made 52253 lb/h (23701,96 kg/HR) carbon monoxide and 3513 lb/h (1593,5 kg/h) of hydrogen. These gases, together with the hydrogen produced in the electrolysis unit 10, and 4527 lb/h (2053,45 kg/h) of hydrogen produced in isobutilene synthesizer, came into the synthesizer of methanol. In a reactor for the production of gas 100 filed 24066 lb/h (10916,34 kg/HR) carbon dioxide from ethanol fermenter with a capacity of 100 million litres per year. In addition, in the reactor for the production of gas 100 submitting the carbon monoxide was also filed in the methanol synthesizer 16. The methanol synthesizer 16 made 94723 lb/h (42967,26 kg/h) methanol, which was received in a simple synthesizer ether.

In isobutilene synthesizer filed 171686 lb/h (77876,77 kg/h) of butane to produce 5920 lb/h (2685,31 kg/h) of hydrogen and 165766 lb/h (75191,46 kg/h) of isobutylene. As mentioned above, 4527 lb/h (2053,45 kg/h) of hydrogen was applied in the synthesis of methanol and 1393 lb/h (631,86 kg/h) of hydrogen were sent to the store. The isobutylene and methanol were combined in a simple synthesizer broadcast receiving 260500 lb/h (118162,8 kg/h) MTBE.

Example 3

This example demonstrates the variant shown in Fig. 3, which is an installation for the production of 240 million litres per year of methanol.

84000 lbs/h (38102,4 kg/h) gas or oil N 6, 297577 lb/h (134980,92 kg/HR) of oxygen and 984980 lb/h (445786,92 kg/h) of nitrogen was applied in 80-megawatt sagterious installation 200. Atmospheric air was used as the source of oxygen and nitrogen. 120% oxygen was filed in sagterious installation 200. Installation produced 1.2 million lb/h (544320 kg/h) a pair of 180 psi (12,654 kg/cm2) and exhaust gases. Electricity from agenerase installation and 100 MW from the grid was applied to the electrolysis unit 10 to produce 3800 lb/h (1723,68 kg/h) vtoroe 16, reactor for the production of gas 100, synthesizer simple ether 18 and isobutilene synthesizer same as in Example 2.

Exhaust gases from agenerase installation 200 contain mixed flows of oxygen, nitrogen, carbon dioxide, water vapor and sulfur particles, which were divided in the installation of flue gas cleaning 278 as follows. Gas cleaning of waste gases produced 984980 lb/h (446786,92 kg/h) of nitrogen and 49596 lb/h (22496,75 kg/HR) of oxygen that was released into the atmosphere. Were also produced 75600 lb/h (34292,16 kg/h) of water and 2500 lb/h sulfur specimens (1134 kg/h), which were processed in the installation of water treatment. Installation of water treatment /wash installation (received 252787 lb/h (114664,18 kg/HR) carbon dioxide.

1. Synergistic method for the production of methanol comprising the steps: a) electrolysis of water to produce hydrogen and oxygen; b) providing a supply current to the organic combustible fuel; C) feeding at least part of the oxygen obtained in stage a), together with the stoichiometric quantity mentioned organic combustible fuel in a partial oxidation reactor for receiving exhaust gases containing carbon monoxide and hydrogen; d) feeding at least the additional hydrogen in the synthesis of methanol to provide the stoichiometric supply of hydrogen and carbon monoxide mentioned methanol synthesizer.

2. The process under item 1, characterized in that the fuel is heavy oil, having a boiling point higher than about 650oF(343, 33oC).

3. The process under item 2, characterized in that the said heavy oil has a boiling point higher than about 1000oF (537, 78oC).

4. The process under item 2, characterized in that it further includes the step of reforming at least part of the above-mentioned methanol in the methanol reformer obtaining methyl tert-butyl ether.

5. The process under item 4, characterized in that it further includes the following steps: a) connecting a pair and butane in isobutilene synthesizer to produce hydrogen and isobutylene and (b) feeding at least part of the above-mentioned isobutylene in the above-mentioned methanol reformer obtaining mentioned methyl tert-butyl ether.

6. The process under item 1, characterized in that the additional hydrogen, which serves in the above-mentioned methanol synthesizer obtained in stage a) p. 1.

7. The process under item 5, characterized in that said additional hydrogen, which serves in the above-mentioned synthesis of methanol, are selected from hydrogen obtained by electrolysis in step (a) p. 1, hydrogen, pram, which further includes the steps of: a) providing a feed stream of carbon dioxide; b) heating said carbon dioxide to a temperature above the temperature of dissociation of said carbon dioxide to obtain carbon monoxide, and C) feeding at least part of said carbon monoxide obtained in step b), in the above-mentioned synthesis of methanol.

9. The process under item 8, characterized in that the process also includes the steps of: a) adding steam and alcohol predecessor in the fermenter for ethanol; b) reforming at least part of the above-mentioned ethanol to obtain ethyl tert-butyl ether and C) feeding at least part of the mentioned Dookie carbon of the mentioned fermenter in said reactor of step a) p. 8.

10. The process under item 1, characterized in that it further includes the steps of: a) adding steam and alcohol predecessor in the fermenter for ethanol and b) reforming at least part of the above-mentioned ethanol to obtain ethyl tert-butyl ether.

11. The process under item 1, characterized in that it further includes the steps: a) providing a first feed stream containing organic combustible fuel; b) providing a second pithouses the actor for burning mentioned first feed stream and produce steam, electricity and flue gas containing carbon dioxide; and g) using at least part of the electricity for the electrolysis of water at the stage a) p. 1.

12. The process under item 11, characterized in that it further includes the steps of: a) processing mentioned flue gases for a first stream comprising sulfur-containing compounds and water vapor, and a second stream containing carbon dioxide; and b) feeding at least part of the mentioned second thread in said agenerase reactor.

13. The process under item 12, characterized in that the said agenerase the reactor is the only cycle with a steam boiler, and said second thread serves in the above-mentioned steam boiler.

14. The process under item 12, characterized in that the said agenerase reactor is combined cycle with turbine internal combustion, and said second thread serves in the above-mentioned turbine internal combustion engines.

15. The process under item 12, characterized in that it further includes an air separation unit to obtain a first stream containing oxygen, and a second stream containing nitrogen and at least part of these Pervov the second stream consists of essentially pure Dookie carbon.

17. The process under item 11, characterized in that it further includes the steps of: a) providing a feed stream of carbon dioxide; b) heating said carbon dioxide to a temperature above the temperature of dissociation of said carbon dioxide to obtain carbon monoxide, and C) feeding at least part of said carbon monoxide obtained in step b) in the above-mentioned synthesis of methanol.

18. The process under item 17, characterized in that the carbon dioxide separated from the aforementioned flue gases and served in said reactor of step a) p. 17.

19. The process under item 5, characterized in that the exhaust gases also include hydrogen and said hydrogen is separated from the exhaust gases.

20. The process under item 5, characterized in that it further includes the steps of: a) providing a feed stream of carbon dioxide; b) heating said carbon dioxide to a temperature above the temperature of dissociation of said carbon dioxide to obtain carbon monoxide, and C) feeding at least part of said carbon monoxide obtained in step a), in the above-mentioned synthesis of methanol.

21. The process according to p. 20, characterized in that the hydrogen, which serves in the above-mentioned synthesis of the a, produced in the above-mentioned isobutilene synthesizer, or combinations thereof.

22. The process according to p. 21, characterized in that it further includes the steps of: a) adding steam and alcohol predecessor in the fermenter for ethanol and carbon dioxide, (b) the allocation referred to carbon dioxide and C) feeding said carbon dioxide in said reactor of step a) p. 15.

23. The process according to p. 21, characterized in that it further includes the steps of: a) adding steam and alcohol predecessor in the fermenter for ethanol and carbon dioxide; b) reforming at least part of the above-mentioned ethanol to obtain ethyl tert-butyl ether.

24. The process p. 23, characterized in that it further includes the steps: a) selection of the aforementioned carbon dioxide obtained in the above-mentioned fermenter, and b) the supply of carbon dioxide selected from the group comprising carbon dioxide from the above fermenter, carbon dioxide from the aforementioned flue gas or of a mixture in said reactor of step a) p. 20.

25. Synergistic method for the production of methanol comprising the steps: a) electrolysis of water to produce hydrogen and oxygen, (b) providing a feed stream org is americasteam number mentioned organic combustible fuel in a partial oxidation reactor to produce exhaust gases, including carbon monoxide and hydrogen; d) providing a feed stream of carbon dioxide for cooling the above-mentioned partial oxidation reactor in order to increase the temperature of said carbon dioxide to a temperature above the temperature of dissociation of said carbon dioxide to obtain carbon monoxide and oxygen; d) feeding said carbon monoxide and oxygen, obtained in stage d), said reactor for partial oxidation to obtain additional quantities of carbon monoxide, hydrogen and heat; (e) feeding at least part of said carbon monoxide and hydrogen in the synthesis of methanol for the production of methanol and W) adding additional hydrogen in the synthesis of methanol to provide the stoichiometric supply of hydrogen and carbon monoxide mentioned methanol synthesizer.

26. The process p. 25, characterized in that said carbon dioxide is also used for cooling the exhaust gases of the above-mentioned partial oxidation reactor.

27. Synergistic method for the production of methanol comprising the steps: a) electrolysis of water to produce hydrogen and oxygen; b) providing a feed stream dioxide plastics technology: turning & carbon to obtain carbon monoxide and g) supply the stoichiometric amount of carbon monoxide and hydrogen in the synthesis of methanol for the production of methanol, these stoichiometric amount of gain through the use of at least part of the carbon monoxide prepared by step b), above, and at least part of the hydrogen, prepared by step (a) above.

28. The process according to p. 27, characterized in that it further includes the step of reforming at least part of the above-mentioned methanol in the methanol reformer obtaining tert-butyl ether.

29. The process p. 28, characterized in that it further includes the steps of: a) combining a pair and butane in isobutilene synthesizer to produce hydrogen and isobutylene and (b) feeding at least part of the above-mentioned isobutylene in the above-mentioned methylene reformer to get mentioned methyl tert-butyl ether.

30. The process according to p. 29, characterized in that the hydrogen, which serves in the above-mentioned synthesis of methanol, are selected from hydrogen, obtained by carrying out the above-mentioned electrolysis in step (a) p. 22, and hydrogen produced mentioned isobutilene synthesizer, or mixtures thereof.

31. The process p. 30, characterized in that it further includes the steps of: a) adding a pair of what ina least part of the above-mentioned ethanol to obtain ethyl tert-butyl ether.

32. The process under item 31, wherein at least part of the carbon dioxide produced in the above-mentioned fermenter, used for preparation of the feed stream b) p. 27.

33. The process according to p. 27, characterized in that it further includes the steps of: a) adding steam and alcohol predecessor in the fermenter for ethanol and carbon dioxide and (b) reforming at least part of the above-mentioned ethanol to obtain ethyl tert-butyl ether.

34. The process under item 33, characterized in that at least part of the carbon dioxide produced in the above-mentioned fermenter, used for preparation of the feed stream b) p. 27.

 

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