CN102180767A - Method and device for jointly producing methanol, ammonia and acetic acid by using coal and natural gas - Google Patents
Method and device for jointly producing methanol, ammonia and acetic acid by using coal and natural gas Download PDFInfo
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Abstract
The invention provides a method and a device for jointly producing methanol, ammonia and acetic acid by using coal and natural gas. The method comprises the following steps of: preparing first synthetic gas from the natural gas serving as a raw material and preparing second synthetic gas from the coal serving as a raw material; extracting carbon monoxide from the first synthetic gas or the second synthetic gas; introducing the first synthetic gas and the second synthetic gas from which the carbon monoxide is extracted in the preset ratio into a methanol synthesizer to prepare the methanol; introducing the methanol and the carbon monoxide in the preset ratio into an acetic acid synthesizer to prepare the acetic acid; extracting hydrogen from purge gas obtained in the preparation of the methanol; and introducing nitrogen and the hydrogen in the preset ratio into an ammonia synthesizer to prepare the ammonia. By the coal and natural gas combined scheme, the problems of high carbon content and low hydrogen content in the synthetic gas prepared from coal, and low carbon content and high hydrogen content in the synthetic gas prepared from natural gas are solved; and according to reasonable blending of various resources, the various resources are utilized fully, the products are diversified, the utilization ratio of the resources is high and the production cost is low.
Description
Technical field
The present invention relates to chemical technology field, relate in particular to the method and the device of a kind of coal and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid.
Background technology
Synthetic gas is a kind of gas mixture that is rich in hydrogen and carbon monoxide, has quite widely as the raw material of petroleum chemicals and uses.The application of synthetic gas can roughly be divided into three kinds: a kind of is the hydrogen that utilizes in the synthetic gas, as synthetic ammonia, refinery hydrogen preparing etc.; A kind of is hydrogen and the carbon monoxide that utilizes simultaneously in the synthetic gas, as preparation methyl alcohol, oxo alcohol etc.; Also has a kind of carbon monoxide that mainly utilizes in the synthetic gas, as preparing acetic acid etc.
Theoretically, the every material that contains these two kinds of elements of C, H of occurring in nature can be as the raw material of synthetic gas, as Sweet natural gas, coal, hydro carbons or biomass etc.Different according to raw material and equipment, synthesis gas preparation technology can be divided into different types, present most of synthesis gas preparation technology with Sweet natural gas and coal as raw material.
The technology that present sophisticated conversion of natural gas prepares synthetic gas can be divided into steam reforming, partial oxidation process and the two three major types such as combined method.With the Sweet natural gas is the technology of feedstock production synthetic gas, and its principal feature is that flow process is short, CO
2Quantity discharged is few etc., but also exists investment high simultaneously, to shortcomings such as Gas Prices sensitivity, catalyzer costliness and the easy inactivations of high temperature.When being the feedstock production synthetic gas with the Sweet natural gas, the theoretical ratio that methane and water vapour reaction generate hydrogen and carbon monoxide is 3.0.
With the coal is the technology of feedstock production synthetic gas, can be divided into bed technology, fluidization and air flow bed technology.In numerous coal gasifying process, Lurgi pressurized gasification technology belongs to pressurization static bed gasification technology; U.S. U-gas Coal Gasification Technology and Shanxi Coal-Chemical Inst., Chinese Academy of Sciences carry out the Unit of Coal Gasification for Pulverized Coal with Ash technology and belong to the fluidized-bed gasification technology, and the multi-nozzle opposed type coal water slurry gasification technology of texaco gasification technology and East China University of Science belongs to the wet entrained flow bed gasification technology; The Shell gasifying process is the dry method fine coal pressurized air flow bed gasification technology by shell International Petroleum Company exploitation, and the GSP gasification technology of German future source of energy company exploitation also belongs to entrained flow bed gasification technology.With the coal is in the synthetic gas of feedstock production, hydrogen-carbon ratio (H
2-CO
2)/(CO+CO
2) all less than 1, for example: the coal water slurry entrained flow bed synthetic gas classical group that obtains becomes H
230～40%, CO 45～55%, CO
215～20%; The pressurised fluidized bed synthetic gas classical group that obtains of dry coal powder becomes H
225～35%, CO 55～65%, CO
22～5%.
From to being used to of synthetic gas, each derived product all has separately requirement to the component of synthetic gas.In methyl alcohol synthetic, H
2With the theoretical molar ratio of CO be 2.0, the hydrogen-carbon ratio (H of control in the synthetic gas in actual production
2-CO
2)/(CO+CO
2)=2.05～2.10, CO
2Content about 3.5%.By forming as can be known of above-mentioned synthetic gas, when with the Sweet natural gas being raw material generation methyl alcohol, need unnecessary hydrogen is burnt in converter to be met the synthetic gas of the synthetic desired ratio of carbon-hydrogen of methyl alcohol, wasted a large amount of hydrogen resources like this.And with the coal be hydrogen-carbon ratio in the synthetic gas that obtains of raw material less than the synthetic desired hydrogen-carbon ratio of methyl alcohol, in generative process, need by CO conversion and decarbonization system unnecessary carbon with CO
2Form remove, make the hydrogen-carbon ratio in the synthetic gas satisfy the requirement of methyl alcohol synthetic, make the production cost height thus, and caused the waste of a large amount of carbon resources.
In ammonia synthesizing industry, need further process synthetic gas, promptly by the CO transformationreation, obtaining more hydrogen, and the CO that obtains after the conversion
2Must remove, can not in synthetic ammonia, obtain utilizing.In the technology of acetic acid synthesis from methanol carbonylation, as raw material, can cause the waste of a large amount of hydrogen resources with synthetic gas.
By above-mentioned analysis as can be known, in process, all there is the unbalanced problem of hydrogen carbon, can causes the waste of part available gas, thus, need provide new technology, to realize the optimal utilization of the energy with synthesis gas preparation methyl alcohol, acetic acid and synthetic ammonia.
Summary of the invention
The embodiment of the invention provides the method and the device of a kind of coal and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, and the different synthetic gas of forming of reasonable use are produced methyl alcohol, ammonia and acetic acid, with the optimization utilization that realizes raw material, cut down the consumption of energy, increase economic efficiency.
The embodiment of the invention provides the method for a kind of coal and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, comprising:
With the Sweet natural gas is first strand of synthetic gas of feedstock production; With the coal is second strand of synthetic gas of feedstock production;
From described first strand of synthetic gas or described second strand of synthetic gas, extract carbon monoxide;
Described first strand of synthetic gas behind the extraction carbon monoxide, preset proportion and described second strand of synthetic gas are fed methanol synthesizer, prepare methyl alcohol;
The described methyl alcohol and the described carbon monoxide of preset proportion are fed the acetic acid synthesizer, prepare acetic acid;
From prepare the off-gas that described methyl alcohol obtains, extract hydrogen, the nitrogen and the described hydrogen of preset proportion is fed synthetic ammonia installation, prepare ammonia.
The embodiment of the invention also provides the method for a kind of coal and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, comprising:
With the Sweet natural gas is first strand of synthetic gas of feedstock production; With the coal is second strand of synthetic gas of feedstock production;
From described first strand of synthetic gas or described second strand of synthetic gas, extract carbon monoxide, and from described first strand of synthetic gas or described second strand of synthetic gas, extract hydrogen;
Described first strand of synthetic gas behind extraction carbon monoxide and the hydrogen, preset proportion and described second strand of synthetic gas are fed methanol synthesizer, prepare methyl alcohol;
The described methyl alcohol and the described carbon monoxide of preset proportion are fed the acetic acid synthesizer, prepare acetic acid;
The nitrogen and the described hydrogen of preset proportion are fed synthetic ammonia installation, prepare ammonia.
The embodiment of the invention provides the device of a kind of coal and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, comprising:
Converter, vapourizing furnace, air separation facility, methanol synthesizer, acetic acid synthesizer, ammonia synthesizer, carbon monoxide tripping device and hydrogen separation device;
The outlet of described converter links to each other with methanol synthesizer respectively with the outlet of described vapourizing furnace;
The oxygen outlet of described air separation facility links to each other with described vapourizing furnace with described converter respectively;
Described carbon monoxide tripping device is connected between the inlet of the outlet of described converter and described methanol synthesizer, and perhaps described carbon monoxide tripping device is connected between the inlet of the outlet of described converter and described methanol synthesizer;
The carbon monoxide outlet of described carbon monoxide tripping device links to each other with the inlet of described acetic acid synthesizer respectively with the outlet of described methanol synthesizer;
Described hydrogen separation device is connected between the inlet of the outlet of described converter and described methanol synthesizer, perhaps described hydrogen separation device is connected between the inlet of the outlet of described vapourizing furnace and described methanol synthesizer, and perhaps described hydrogen separation device is connected between the inlet of the off-gas outlet of described methanol synthesizer and described ammonia synthesizer;
The hydrogen outlet of described hydrogen separation device links to each other with the inlet of described synthetic ammonia installation respectively with the nitrogen outlet of described air separation facility;
Wherein, to be used for the Sweet natural gas be first strand of synthetic gas of feedstock production to described converter; It is second strand of synthetic gas of feedstock production that described vapourizing furnace is used for the coal; Described air separation facility is used for extracting oxygen and nitrogen from air, and described oxygen is offered described converter and described vapourizing furnace, and nitrogen is offered described synthetic ammonia installation.
The coal of the embodiment of the invention and Sweet natural gas combination producing methyl alcohol, the method of ammonia and acetic acid and device, by being first strand of synthetic gas of feedstock production with the Sweet natural gas and being second strand of synthetic gas of feedstock production with the coal, and therefrom extract carbon monoxide and hydrogen, regulate the ratio of two strands of synthetic gas, obtain the fine methyl methanol syngas, and the methyl alcohol of the carbon monoxide of utilization extraction and preparation is acetic acid synthesized, utilize the Preparation of Hydrogen ammonia of nitrogen and extraction, thus reasonable use the synthetic gas of different compositions produce methyl alcohol, ammonia and acetic acid, overcome the unbalanced problem of hydrogen carbon that products such as coal and Sweet natural gas system methyl alcohol exist, realized the optimization utilization of raw material, the reduction of energy consumption and recycling economy.
Description of drawings
Fig. 1 is the schema of the method embodiment one of coal of the present invention and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid;
Fig. 2 is the process flow sheet of the method embodiment two of coal of the present invention and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid;
Fig. 3 is the schema of the method embodiment three of coal of the present invention and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid;
Fig. 4 is the process flow sheet of the method embodiment four of coal of the present invention and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid.
Embodiment
For the purpose, technical scheme and the advantage that make the embodiment of the invention clearer, below in conjunction with the accompanying drawing in the embodiment of the invention, technical scheme in the embodiment of the invention is clearly and completely described, obviously, described embodiment is the present invention's part embodiment, rather than whole embodiment.Based on the embodiment among the present invention, those of ordinary skills belong to the scope of protection of the invention not making the every other embodiment that is obtained under the creative work prerequisite.
Fig. 1 is the schema of the method embodiment one of coal of the present invention and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, and as shown in Figure 1, this method comprises:
Be raw material with Sweet natural gas and coal respectively, adopt existing mature technology to prepare synthetic gas, for example: when being raw material, can adopt steam reforming or partial oxidation process with the Sweet natural gas; When being raw material, can adopt Coal Gasification Technology, and the raw gas that will obtain by gasification, can pass through portion C O conversion and purification, adjust the composition of coal gas and remove wherein sulphur and CO with the coal
2Deng impurity, obtain synthetic gas.The synthetic gas that with the Sweet natural gas is feedstock production is called first strand of synthetic gas, is that the synthetic gas of feedstock production is called second strand of synthetic gas with the coal.When being the feedstock production synthetic gas with Sweet natural gas and coal, all need oxygen, required oxygen can be provided by air separation facility.
In the present embodiment, the required carbon monoxide of preparation acetic acid can extract from first strand of synthetic gas, also can extract from second strand of synthetic gas.Extract carbon monoxide concrete steps can for: first strand of synthetic gas of part or second strand of synthetic gas of part are fed the carbon monoxide tripping device, extract carbon monoxide.
Further, if technology whenever necessary, for example: in order to obtain more fine methyl methanol syngas, promptly for the more excellent methyl methanol syngas of the content that obtains carbon, hydrogen, carbonic acid gas, can be before extracting carbon monoxide, remove carbonic acid gas in first strand of synthetic gas or the second strand of synthetic gas by existing decarburization technique.
With extracting first strand of synthetic gas and second strand of synthetic gas of carbon monoxide, with the mixed that presets, feed methanol synthesizer, prepare methyl alcohol; Wherein, this ratio that presets is for making the hydrogen-carbon ratio in the synthetic gas that feeds methanol synthesizer reach 2.05～2.10, and this methanol synthesizer can be the device of sophisticated preparation methyl alcohol in the prior art, does not repeat them here.
With methyl alcohol for preparing in the above-mentioned steps and the carbon monoxide that from synthetic gas, extracts, feed the acetic acid synthesizer with the ratio that presets; Wherein, this ratio that presets is for making the mixture that feeds the acetic acid synthesizer reach acetic acid synthesized requirement, and this acetic acid synthesizer can be the device of existing sophisticated preparation acetic acid, does not repeat them here.
The off-gas that preparation methyl alcohol is obtained feeds hydrogen separation device, extracts hydrogen; And off-gas extracted the tail gas that obtains behind the hydrogen fuel as first strand of synthetic gas of preparation.
Nitrogen that air separation facility is extracted from air and the hydrogen that extracts from off-gas feed synthetic ammonia installation with the ratio that presets; Wherein, this ratio that presets is for making the mixture that feeds synthetic ammonia installation reach the requirement of synthetic ammonia, and this synthetic ammonia installation is the device of sophisticated preparation ammonia in the prior art, does not repeat them here.
Wherein, present embodiment does not limit the sequential relationship of above steps, and above steps only represents that the present invention produces the technical process of methyl alcohol, ammonia and acetic acid.
Present embodiment, by being first strand of synthetic gas of feedstock production with the Sweet natural gas and being second strand of synthetic gas of feedstock production with the coal, and from first strand of synthetic gas or second strand of synthetic gas, extract carbon monoxide, from methanol purge gas, extract hydrogen, regulate the ratio of two strands of synthetic gas, obtain the fine methyl methanol syngas, the carbon monoxide that utilization is extracted and the methyl alcohol of preparation are acetic acid synthesized, utilize the Preparation of Hydrogen ammonia of nitrogen and extraction, thus reasonable use the synthetic gas of different compositions produce methyl alcohol, ammonia and acetic acid, overcome the unbalanced problem of hydrogen carbon that products such as coal and Sweet natural gas system methyl alcohol exist, realized the optimization utilization of raw material, the reduction of energy consumption and recycling economy.
Describe the coal that the inventive method embodiment one provides and the method for Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid in detail below by Fig. 2, Fig. 2 is the process flow sheet of the method embodiment two of coal of the present invention and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, as shown in Figure 2, this method comprises:
Sweet natural gas transforms in converter, obtains synthetic gas 1, and synthetic gas 1 is divided into two strands, i.e. synthetic gas 2 and synthetic gas 3.Synthetic gas 2 can feed decarbonization device and remove wherein CO
2Mix with synthetic gas 3 back, becomes first strand of synthetic gas 4.Wherein, the tolerance of synthetic gas 2 can be adjusted according to arts demand.In addition, the CO that removes of decarbonization device
2Can also turn back to converter and make raw material, to reclaim carbon resource.
Coal transforms in vapourizing furnace and can pass through and obtains second strand of synthetic gas 5 after CO part changing device, refining plant are handled, and wherein, this purifying treatment can adopt the sophisticated raw gas purifying technology that has now, to remove impurity such as wherein sulphur, carbonic acid gas.Air separation facility extracts O from air
2, and with the O that extracts
2Offer converter and vapourizing furnace.
Second strand of synthetic gas 5 can be divided into two strands of synthetic gas, is specially: synthetic gas 6 and synthetic gas 7;
Synthetic gas 9 and synthetic gas 7, synthetic gas 4 are mixed into synthetic gas 10, as the unstripped gas of synthesizing methanol; Wherein, the main component of synthetic gas 10 is: H
2, CO, CO
2, be a kind of high quality raw material gas of synthesizing methanol; Can make the hydrogen-carbon ratio of synthetic gas 10 reach 2.05～2.10 by regulating the tolerance of synthetic gas 4, synthetic gas 7 and synthetic gas 9;
Methyl alcohol with high-purity CO gas 8 and methanol synthesizer prepare feeds the acetic acid synthesizer, with preparation acetic acid;
In the methyl alcohol preparation process, discharge off-gas 11 in the methanol synthesizer, this off-gas 11 is fed hydrogen separation device, to extract H wherein
2The exit gas of hydrogen separation device is: high-purity hydrogen 12 and tail gas 13;
With high-purity hydrogen 12 and N from air separation facility
2After the mixing, feed ammonia synthesizer after the compressed (not shown), with preparation ammonia;
The tail gas 13 that hydrogen separation device is discharged turns back to converter and acts as a fuel, for conversion of natural gas provides heat, to reclaim resource and to cut down the consumption of energy.
Present embodiment is to extract CO in second strand of synthetic gas, but present embodiment does not limit the position that CO extracts.For example: also can in first strand of synthetic gas, extract CO.
The flow of each road gas and pressure are to be decided by preparation methyl alcohol, acetic acid and the required proportioning raw materials of ammonia in the present embodiment, by regulating the flow of each road gas, and can be so that synthetic gas be fully utilized.
The output of methyl alcohol, ammonia and acetic acid can be regulated in the scope of a broad in the present embodiment; By regulating the tolerance of each strand synthetic gas, the output that can regulate methyl alcohol; By the extracted amount of increase and decrease CO, the output that can regulate acetic acid; The output of ammonia can be by increase and decrease H
2Extracted amount regulate.
The method of the coal that present embodiment provides and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, except beneficial effect with the inventive method embodiment one, also have: present embodiment changes in the existing technology the direct emptying of methanol purge gas or makes the way of fuel, but from methanol purge gas, isolate highly purified hydrogen, and with the fuel of the tail gas behind the separating hydrogen gas as conversion of natural gas, not only avoid the waste of hydrogen 7 resources thus, can also reduce the consumption of fuel gas.
Fig. 3 is the schema of the method embodiment three of coal of the present invention and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, and as shown in Figure 3, this method comprises:
Specifically, do not repeat them here referring to the description among the inventive method embodiment one.
In the present embodiment, carbon monoxide that preparation acetic acid is required and the required hydrogen of preparation ammonia can extract from synthetic gas; Wherein, required carbon monoxide and hydrogen can extract from first strand of synthetic gas respectively, also can extract from second strand of synthetic gas; When carbon monoxide and hydrogen all extract from first strand of synthetic gas or second strand of synthetic gas, can extract carbon monoxide earlier, also can extract hydrogen earlier.
Extract carbon monoxide and hydrogen concrete steps can for: first strand of synthetic gas of part or second strand of synthetic gas of part are fed the carbon monoxide tripping device, extract carbon monoxide; First strand of synthetic gas of part or second strand of synthetic gas of part are fed hydrogen separation device, extract hydrogen.
If technology whenever necessary, first strand of synthetic gas can be fed decarbonization device, to remove CO wherein
2The CO that removes
2Can turn back to the raw material of converter, to reclaim carbon resource as conversion of natural gas.
With extracting first strand of synthetic gas and second strand of synthetic gas of carbon monoxide and hydrogen, with the mixed that presets, feed methanol synthesizer, prepare methyl alcohol; Wherein, this ratio that presets reaches 2.05～2.10 for the feasible hydrogen-carbon ratio that feeds the mixture of methanol synthesizer, and this methanol synthesizer is the device of sophisticated preparation methyl alcohol in the prior art, does not repeat them here.
With methyl alcohol for preparing in the above-mentioned steps and the carbon monoxide that from synthetic gas, extracts, feed the acetic acid synthesizer with the ratio that presets; Wherein, this ratio that presets is for making the mixture that feeds the acetic acid synthesizer reach acetic acid synthesized requirement, and this acetic acid synthesizer is the device of sophisticated preparation acetic acid in the prior art, does not repeat them here.
Nitrogen that air separation facility is extracted from air and the hydrogen that extracts from synthetic gas feed synthetic ammonia installation with the ratio that presets; Wherein, this ratio that presets is for making the mixture that feeds synthetic ammonia installation reach the requirement of synthetic ammonia, and this synthetic ammonia installation is the device of sophisticated preparation ammonia in the prior art, does not repeat them here.
Wherein, present embodiment does not limit the sequential relationship of above steps, and above steps only represents that the present invention prepares the technical process of methyl alcohol, ammonia and acetic acid.
Present embodiment, by being first strand of synthetic gas of feedstock production with the Sweet natural gas and being second strand of synthetic gas of feedstock production with the coal, and from first strand of synthetic gas or second strand of synthetic gas, extract carbon monoxide and hydrogen, regulate the ratio of two strands of synthetic gas, obtain the fine methyl methanol syngas, the carbon monoxide that utilization is extracted and the methyl alcohol of preparation are acetic acid synthesized, utilize the Preparation of Hydrogen ammonia of nitrogen and extraction, thus reasonable use the synthetic gas of different compositions produce methyl alcohol, ammonia and acetic acid, overcome the unbalanced problem of hydrogen carbon that products such as coal and Sweet natural gas system methyl alcohol exist, realized the optimization utilization of raw material, the reduction of energy consumption, and improved economic benefit.
Describe the coal that the inventive method embodiment three provides and the method for Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid in detail below by Fig. 4, Fig. 4 is the process flow sheet of the method embodiment four of coal of the present invention and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, as described in Figure 4, this method comprises:
Sweet natural gas is converted into first strand of synthetic gas 21 in converter, airshed for example can be 8548kmol/h, 40 ℃ of temperature, pressure 1.5MPa.Coal gasifies in vapourizing furnace and obtains second strand of synthetic gas 31 through portion C O conversion and purifying treatment, and airshed for example can be 3207kmol/h, 40 ℃ of temperature, pressure 2.8MPa.Air separation facility extracts O from air
2, and with the O that extracts
2Offer converter and vapourizing furnace.
First strand of synthetic gas 21 can be divided into two strands of synthetic gas, is specially: synthetic gas 22 and synthetic gas 23, and wherein, synthetic gas 22 for example accounts for 34.2% of first strand of synthetic gas 21, and synthetic gas 23 for example accounts for 65.8% of first strand of synthetic gas 21;
Carbon monoxide tripping device inlet temperature for example can be 35～45 ℃, and pressure for example can be 1.0～3.0MPa; The exit gas of carbon monoxide tripping device is: high-purity CO gas 25 and the synthetic gas 26 that extracted CO, and wherein, the CO content of high-purity CO gas 25 is for example more than 99.9%, and flow for example can be 602kmol/h; The extracted amount of CO can be adjusted according to the variation of subsequent step consumption;
The flow of synthetic gas 26 for example can be 4479kmol/h, and it is fed hydrogen separation device, to extract H wherein
2Hydrogen separation device import thing temperature for example can be 35～45 ℃, and pressure for example can be 1.0～4.0MPa; The exit gas of hydrogen separation device is: high-purity hydrogen 27 and extracted H
2After synthetic gas 28, wherein, the H of high-purity hydrogen 27
2Content is for example more than 99.9%, and flow can be 1044kmol/h, and synthetic gas 28 is rich carbon gas;
Pressurization synthetic gas 28, synthetic gas 23 and second strand of synthetic gas 31 after the (not shown) is mixed into synthetic gas 32, as unstripped gas to prepare methyl alcohol; Wherein, the flow of synthetic gas 32 for example can be for 9569kmol/h, temperature can be 1.5MPa for 40 ℃, pressure, and main component can be H
267.4%, CO 27.5%, CO
23.7%, hydrogen-carbon ratio is (H
2-CO
2)/(CO+CO
2)=2.04 are a kind of high quality raw material gas of synthesizing methanol;
With synthetic gas 32 (not shown) (for example boosting to 5.4MPa) of boosting, feed methanol synthesizer then, after the thick methyl alcohol that obtains passes through the rectifying (not shown) again, can obtain the refined methanol of 2782kmol/h; The methyl alcohol that obtains can be used as product, also can be used as acetic acid synthesized raw material;
With high-purity hydrogen 27 and N from air separation facility
2After the mixing, feed ammonia synthesizer after the compressed (not shown), with preparation ammonia;
Methyl alcohol with high-purity CO gas 25 and methanol synthesizer prepare feeds the acetic acid synthesizer, with preparation acetic acid.
Present embodiment extracts CO and H in first strand of synthetic gas
2, and present embodiment does not limit the position and the order of CO and H2 extraction.For example: can in second strand of synthetic gas, extract CO and H
2Also can extract CO in one synthetic gas in office, and in another strand synthetic gas, extract H
2As CO and H
2When in one synthetic gas, extracting, CO can be extracted earlier, also H can be extracted earlier
2
Provided concrete flow and the pressure data of each road gas in the present embodiment, this is only as a specific embodiment, and be not restriction to the embodiment of the invention, the flow of each road gas and pressure are to be decided by preparation methyl alcohol, acetic acid and the required proportioning raw materials of ammonia in the present embodiment, by flow and the pressure of regulating each road gas, can be so that synthetic gas be fully utilized.
The output of methyl alcohol, ammonia and acetic acid can be regulated in the scope of a broad in the present embodiment; By regulating the tolerance of each strand synthetic gas, the output that can regulate methyl alcohol; By the extracted amount of increase and decrease CO, the output that can regulate acetic acid; The output of ammonia can be by increase and decrease H
2Extracted amount regulate.
The method of the coal that various embodiments of the present invention provide and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, by coal and Sweet natural gas scheme for combining, solved in the producing synthesis gas from coal in the few and Sweet natural gas preparing synthetic gas of the many hydrogen of carbon carbon how this congenital insufficient problem of hydrogen less, simultaneously, by to various reasonable resources allotments and utilization, realized making full use of of various resources; Various embodiments of the present invention have characteristics such as product is versatile and flexible, resource utilization is high, production cost is low, economic benefits are good, and are specific as follows:
(1) when being raw material system methyl methanol syngas with the coal merely, the many hydrogen of carbon are few, need reduce CO content wherein and improve hydrogen richness by transformationreation, to obtain suitable hydrogen-carbon ratio.From economic angle, be very uneconomic; When being raw material system methyl methanol syngas with the Sweet natural gas merely, the few hydrogen of carbon is many, often needs unnecessary hydrogen is burnt in converter, has wasted a large amount of hydrogen resources like this.And the embodiment of the invention has remedied both congenital deficiencies by producing synthesis gas from coal and the associating of Sweet natural gas preparing synthetic gas; By regulating both tolerance, can mix the methyl methanol syngas that meets the demands; Simultaneously, also can therefrom extract a part of CO and H
2, respectively as acetic acid synthesized and raw material synthetic ammonia; By the complementation of these two kinds of synthetic gas, solved hydrogen carbon balance problem, have good economic benefit.
(2) in existing methanol synthesizer, from the isolated N of air separation facility
2Can't obtain utilizing.And in the embodiment of the invention, will be from the isolated N of air separation facility
2Raw material as synthetic ammonia has made full use of N
2Resource has reduced production cost.
(3) in the embodiment of the invention, with the CO that removes
2Be sent to the conversion of natural gas device as raw material, reclaim carbon resource wherein as much as possible, have good economic benefits.
The embodiment of the invention also provides and has been used to use the coal that the embodiment of the invention provides and the device of Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid.Referring to Fig. 2 and Fig. 4, the device embodiment of coal of the present invention and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid can comprise:
Converter, vapourizing furnace, air separation facility, methanol synthesizer, acetic acid synthesizer, ammonia synthesizer, carbon monoxide tripping device and hydrogen separation device.
The outlet of converter links to each other with methanol synthesizer respectively with the outlet of vapourizing furnace.
The oxygen outlet of air separation facility links to each other with vapourizing furnace with converter respectively.
The carbon monoxide tripping device is connected between the inlet of the outlet of converter and methanol synthesizer, and perhaps the carbon monoxide tripping device is connected between the inlet of the outlet of vapourizing furnace and methanol synthesizer.The carbon monoxide outlet of carbon monoxide tripping device links to each other with the inlet of acetic acid synthesizer respectively with the outlet of methanol synthesizer.
Hydrogen separation device is connected between the inlet of the outlet of converter and methanol synthesizer, perhaps hydrogen separation device is connected between the inlet of the outlet of vapourizing furnace and methanol synthesizer, and perhaps hydrogen separation device is connected between the inlet of the off-gas outlet of methanol synthesizer and ammonia synthesizer.The hydrogen outlet of hydrogen separation device links to each other with the inlet of synthetic ammonia installation respectively with the nitrogen outlet of air separation facility.
Further, this device embodiment can also comprise: carbon monoxide conversion device and refining plant.Concrete, carbon monoxide conversion device and refining plant are connected between vapourizing furnace and the carbon monoxide tripping device in turn, are used for the vapourizing furnace expellant gas is carried out carbon monodixe conversion and purification.
Wherein, to be used for the Sweet natural gas be first strand of synthetic gas of feedstock production to converter; It is second strand of synthetic gas of feedstock production that vapourizing furnace is used for the coal; Air separation facility is used for extracting oxygen and nitrogen from air, and oxygen is offered converter and vapourizing furnace, and nitrogen is offered synthetic ammonia installation.On the basis of present embodiment, this device can also comprise: decarbonization device.This decarbonization device is connected between the inlet of the outlet of converter and methanol synthesizer; Perhaps, decarbonization device is connected between the inlet of the outlet of vapourizing furnace and methanol synthesizer.
On the basis of present embodiment, the outlet of the off-gas of methanol synthesizer can link to each other with the inlet of converter; Perhaps, the off-gas outlet of methanol synthesizer links to each other with the inlet of converter by hydrogen separation device, the off-gas outlet that is methanol synthesizer links to each other with the inlet of hydrogen separation device, the outlet of the tail gas of hydrogen separation device links to each other with the inlet of converter, so that the tail gas of getting rid of from hydrogen separation device is as the fuel for preparing first strand of synthetic gas.
The method of device production methyl alcohol, ammonia and acetic acid in the use present embodiment and flow process do not repeat them here referring to the description among each method embodiment of the present invention.
The device that uses present embodiment to provide can use following method to produce methyl alcohol, ammonia and acetic acid: by using with Sweet natural gas as first strand of synthetic gas of feedstock production with the second strand synthetic gas of coal as feedstock production, to prepare methyl alcohol with the ratio that presets; And from first strand of synthetic gas or second strand of synthetic gas, extract carbon monoxide, from first strand of synthetic gas, second strand of synthetic gas or methanol purge gas, extract hydrogen, the carbon monoxide that utilization is extracted and the methyl alcohol of preparation are acetic acid synthesized, utilize the Preparation of Hydrogen ammonia of nitrogen and extraction, thus reasonable use the synthetic gas of different compositions produce methyl alcohol, ammonia and acetic acid, realize the optimization utilization of raw material, the reduction of energy consumption, and improved economic benefit.
It should be noted that at last: above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that: it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement; And these modifications or replacement do not make the essence of appropriate technical solution break away from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1. the method for a coal and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid is characterized in that, comprising:
With the Sweet natural gas is first strand of synthetic gas of feedstock production; With the coal is second strand of synthetic gas of feedstock production;
From described first strand of synthetic gas or described second strand of synthetic gas, extract carbon monoxide;
Described first strand of synthetic gas behind the extraction carbon monoxide, preset proportion and described second strand of synthetic gas are fed methanol synthesizer, prepare methyl alcohol;
The described methyl alcohol and the described carbon monoxide of preset proportion are fed the acetic acid synthesizer, prepare acetic acid;
From prepare the off-gas that described methyl alcohol obtains, extract hydrogen, the nitrogen and the described hydrogen of preset proportion is fed synthetic ammonia installation, prepare ammonia.
2. the method for coal according to claim 1 and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid is characterized in that, also comprises extract carbon monoxide from described first strand of synthetic gas or described second strand of synthetic gas before:
Remove the carbonic acid gas in described first strand of synthetic gas or the described second strand of synthetic gas.
3. the method for coal according to claim 2 and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid is characterized in that, also comprises:
With the described carbonic acid gas that removes raw material as the described first strand of synthetic gas of preparation.
4. according to the method for the arbitrary described coal of claim 1-3 and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, it is characterized in that:
Describedly also comprise after from prepare the off-gas that described methyl alcohol obtains, extracting hydrogen: described off-gas is extracted the tail gas that obtains behind the hydrogen fuel as the described first strand of synthetic gas of preparation.
5. the method for a coal and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid is characterized in that, comprising:
With the Sweet natural gas is first strand of synthetic gas of feedstock production; With the coal is second strand of synthetic gas of feedstock production;
From described first strand of synthetic gas or described second strand of synthetic gas, extract carbon monoxide, and from described first strand of synthetic gas or described second strand of synthetic gas, extract hydrogen;
Described first strand of synthetic gas behind extraction carbon monoxide and the hydrogen, preset proportion and described second strand of synthetic gas are fed methanol synthesizer, prepare methyl alcohol;
The described methyl alcohol and the described carbon monoxide of preset proportion are fed the acetic acid synthesizer, prepare acetic acid;
The nitrogen and the described hydrogen of preset proportion are fed synthetic ammonia installation, prepare ammonia.
6. the method for coal according to claim 5 and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid is characterized in that:
The described carbon monoxide that extracts from described first strand of synthetic gas or described second strand of synthetic gas comprises: described first strand of synthetic gas of part or the described second strand of synthetic gas of part are fed the carbon monoxide tripping device, extract carbon monoxide;
The described hydrogen that extracts from described first strand of synthetic gas or described second strand of synthetic gas comprises: described first strand of synthetic gas of part or the described second strand of synthetic gas of part are fed hydrogen separation device, extract hydrogen.
7. according to the method for claim 5 or 6 described coals and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid, it is characterized in that, from described first strand of synthetic gas or described second strand of synthetic gas, extracting carbon monoxide, and also comprising before from described first strand of synthetic gas or described second strand of synthetic gas, extracting hydrogen:
Remove the carbonic acid gas in described first strand of synthetic gas or the described second strand of synthetic gas, with the described carbonic acid gas that removes raw material as the described first strand of synthetic gas of preparation.
8. the device of a coal and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid is characterized in that, comprising:
Converter, vapourizing furnace, air separation facility, methanol synthesizer, acetic acid synthesizer, ammonia synthesizer, carbon monoxide tripping device and hydrogen separation device;
The outlet of described converter links to each other with described methanol synthesizer respectively with the outlet of described vapourizing furnace;
The oxygen outlet of described air separation facility links to each other with described vapourizing furnace with described converter respectively;
Described carbon monoxide tripping device is connected between the inlet of the outlet of described converter and described methanol synthesizer, and perhaps described carbon monoxide tripping device is connected between the inlet of the outlet of described vapourizing furnace and described methanol synthesizer;
The carbon monoxide outlet of described carbon monoxide tripping device links to each other with the inlet of described acetic acid synthesizer respectively with the outlet of described methanol synthesizer;
Described hydrogen separation device is connected between the inlet of the outlet of described converter and described methanol synthesizer, perhaps described hydrogen separation device is connected between the inlet of the outlet of described vapourizing furnace and described methanol synthesizer, and perhaps described hydrogen separation device is connected between the inlet of the off-gas outlet of described methanol synthesizer and described ammonia synthesizer;
The hydrogen outlet of described hydrogen separation device links to each other with the inlet of described synthetic ammonia installation respectively with the nitrogen outlet of described air separation facility;
Wherein, to be used for the Sweet natural gas be first strand of synthetic gas of feedstock production to described converter; It is second strand of synthetic gas of feedstock production that described vapourizing furnace is used for the coal; Described air separation facility is used for extracting oxygen and nitrogen from air, and described oxygen is offered described converter and described vapourizing furnace, and nitrogen is offered described synthetic ammonia installation.
9. the device of coal according to claim 8 and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid is characterized in that, also comprises: decarbonization device;
Described decarbonization device is connected between the inlet of the outlet of described converter and described methanol synthesizer; Perhaps
Described decarbonization device is connected between the inlet of the outlet of described vapourizing furnace and described methanol synthesizer.
10. the device of coal according to claim 8 and Sweet natural gas combination producing methyl alcohol, ammonia and acetic acid is characterized in that, the off-gas outlet of described methanol synthesizer links to each other with the inlet of described converter; Perhaps the outlet of the tail gas of described hydrogen separation device links to each other with the inlet of described converter.
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Application publication date: 20110914 |