• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    process to produce ammonia synthase gas. the present invention is related to a process for producing ammonia synthase gas, from a hydrocarbon-containing raw material, comprising primary reform steps, secondary reform with an oxidizing current, and further treatment of synthase gas, including modification, carbon dioxide removal and methanation, in which the synthase gas released by the secondary reform is subjected to medium temperature change (mts), at a temperature between 200 and 350 <198> c, and the primary reform is operated with a proportion of steam to carbon less than 2. a corresponding method of remodeling an ammonia facility is disclosed, where an existing hts reactor is modified, to operate at medium temperature, or to be replaced by a new mts reactor, and the proportion of carbon vapor in the primary reformer is lowered to a value in the range of 1.5-2, thereby reducing the inert vapor in the flow velocity through the equipment from previous steps.
    公开号:BR112013000357B1
    申请号:R112013000357-0
    申请日:2011-05-12
    公开日:2020-01-07
    发明作者:Ermanno Filippi；Francesco Baratto；Sergio Panza；Raffaele Ostuni
    申请人:Casale Sa；
    IPC主号:
    专利说明:

    “PROCESS TO PRODUCE AMMONIA SYNTHESIS GAS AND METHOD FOR REMODELING AN AMMONIA INSTALLATION Technical Field of the Invention [001] The present invention relates to the reform of hydrocarbons, to prepare synthesis gas for ammonia production.
    Description of the State of the Art [002] The synthesis of ammonia (NH3) requires a synthesis gas comprising hydrogen (H2) and nitrogen (N2) in an adequate ratio of about 3: 1. The term ammonia synthesis gas will be used with reference to a synthesis gas of the composition mentioned above.
    [003] The production of said synthesis gas is known from the reform of a hydrocarbon raw material (HC) containing methane. The reform takes place in a primary reformer and then in a secondary reformer. Normally, the raw material and an adequate amount of steam are admitted into a primary reformer, in which methane is converted into a mixture of carbon monoxide, carbon dioxide and hydrogen, by passing over an appropriate catalyst; the secondary reformer receives the gaseous product released from the primary reformer and an air flow. The reformed gas leaving the secondary reformer is then purified, especially to remove carbon oxides, CO and CO2, and residual methane, and to obtain an adequate gas composition for ammonia synthesis, having a molar ratio of H2 / N2 (HN ratio) close to 3: 1. In a typical state-of-the-art arrangement, gas is treated in a series of equipment, including a converter
    Petition 870190043784, of 05/09/2019, p. 6/23
    2/13 high temperature change (HTS), normally operating at temperatures in the range 350-500 ° C, a
    converter change of low temperature (LTS), a wash column CO2 and a reactor in methanation • [004] The patent U.S. 4. 910,007 describes one process to product ammonia comprising The
    formation of ammonia synthesis gas by reaction of a carbonaceous raw material with steam and a gas containing oxygen and nitrogen, according to the state of the art.
    [005] The primary reformer converts methane (CH4) and steam (H2O) into CO and H2. The chemical reaction will require one mole of steam for each mole of methane. In practice, the primary reformer is always operated with a higher vapor to carbon (SC) ratio, greater than 2.6 and usually in the range of 2.8-3.5. The reason for choosing the S / C ratio always greater than 2.6 is that the HTS converter requires a vapor to gas ratio greater than 0.4 to avoid excess reduction and hydrocarbon formation by Fischer-Tropsch synthesis . A vapor to gas ratio of about 0.4 in the HTS converter corresponds to a SC ratio of about 2.6 at the input of the primary reformer. Consequently, the supply of steam and methane admitted to the primary reformer must guarantee a proportion of SC greater than or equal to said limit value of 2.6.
    [006] Excess steam - compared to the theoretical stoichiometric value - has the beneficial effect to correct the conversion balance deviation, that is, to assist the conversion of methane.
    Petition 870190043784, of 05/09/2019, p. 7/23
    3/13
    However, a large amount of steam causes the following drawbacks: excess steam causes a higher volumetric flow, which requires larger and more expensive equipment; in addition, excess steam is inert to the reform and therefore has a negative impact on the efficiency of the reform itself. A fraction of the reformer's heat input is actually consumed to heat the inert steam.
    Summary of the Invention [007] The present Applicant has found that the vapor to carbon ratio (S / C ratio or SC ratio) can be modified to unexpectedly low values, notably values below 2.0, preferably values in the range of 1 , 5 - 1,7, when the synthesis gas obtained after a secondary reform process is subjected to an average temperature change reaction, in the presence of an appropriate catalyst, instead of a high temperature change. Said average temperature is in the range of 200 - 350 ° C, preferably in the range of 220 - 310 ° C, more preferably, around 260 - 270 ° C. An appropriate catalyst can be a Cu-Zn catalyst.
    [008] An advantage of such a low proportion of SC is that the volumetric flow through the primary reformer and secondary reformer is markedly reduced. On a theoretical basis, reducing the SC ratio from 3.0 to about 1.5 means that the gas flow is reduced by 60%.
    [009] Consequently, one aspect of the invention relates to a process for producing gas
    Petition 870190043784, of 05/09/2019, p. 8/23
    4/13 synthesis of ammonia from a raw material containing hydrocarbon, the process comprising the stages of primary reform of said raw material containing hydrocarbon with steam and secondary reform with an oxidizing current, the process being characterized by the fact that :
    - the synthesis gas produced by said secondary reform is subjected to an average temperature change, at a temperature between 200 and 350 ° C; and
    - said primary reform is operated with a vapor to carbon ratio of less than 2.0.
    [010] It is preferred that a pre-reform is operated before the primary reform step, in particular with lower vapor to carbon (SC) ratios, close to 1.5. The purpose of pre-reform is to ensure that the primary reform takes place in the presence of a certain amount of hydrogen (H2), to avoid cracking methane.
    [011] Said oxidizing current fed to the secondary reform process can be air, air enriched with O2 or substantially pure oxygen. When the secondary reform process is supplied with air, an excess of nitrogen is normally produced in the synthesis gas, compared to the stoichiometric ratio of 3: 1. Feeding the secondary reform process with air enriched with O2 or substantially pure oxygen has the advantage of reducing or avoiding said excess nitrogen in the reformed gas. When appropriate, nitrogen can be supplied to the purified synthesis gas, notably after the treatment of
    Petition 870190043784, of 05/09/2019, p. 9/23
    5/13 synthesis gas purification to obtain the required HN ratio for ammonia synthesis.
    [012] A preferred range for the SC ratio in the primary reformer is 1.5 - 2.0, with a more preferred range of 1.5 - 1.7.
    [013] Operation with a low SC ratio can cause the synthesis gas to contain a certain amount of unreacted hydrocarbon, in particular, unreacted CH4. According to other aspects of the invention, said unreacted hydrocarbon is at least partially removed from the synthesis gas by:
    - cryogenic separation;
    - an adsorption treatment step, such as, for example, a PSA procedure; or
    - increase in the amount of purge gas removed from the ammonia synthesis circuit, where the synthesis gas produced according to the invention is reacted. Inert gases and methane can be removed from the purge gas using a known treatment, for example, a cryogenic process operated at substantially the same pressure as the synthesis circuit.
    [014] Said cryogenic separation can be performed to remove unreacted methane and also remove excess nitrogen, when the secondary reform process is supplied with air. Increasing the amount of purging in the circuit may be preferred when the oxidizing agent for the secondary reform process is supplied in the form of enriched air or pure oxygen.
    [015] One aspect of the invention also includes a device for producing synthesis gas from
    Petition 870190043784, of 05/09/2019, p. 10/23
    6/13 ammonia, adapted to operate according to the above process.
    [016] The invention is also suitable for remodeling an existing ammonia plant and, in particular, for remodeling the initial steps of the plant. The invention provides a method for remodeling an ammonia plant, comprising processing steps for producing an ammonia synthesis gas, and a synthesis circuit for reacting said ammonia synthesis gas, said process steps comprising at least one reformer primary, a secondary reformer, a high temperature change reactor and a low temperature change reactor arranged downstream of the secondary reformer, to remove carbon oxides from the ammonia synthesis gas, the primary reformer being connected with a hydrocarbon feed and a steam supply. The remodeling method comprises at least the steps of:
    - replace said HTS reactor with a medium temperature change reactor, or modify the HTS reactor for operation at medium temperature, said average temperature being 200 to 350 ° C;
    - modify the hydrocarbon feed and steam feed for the primary reformer, in order to obtain the operation of said primary reformer with a vapor to carbon ratio of less than 2.0, preferably in a range of 1.5 to 2, 0.
    [017] The medium temperature change reactor is adapted with a suitable catalyst for
    Petition 870190043784, of 05/09/2019, p. 11/23
    7/13 operation at said average temperature. Said reactor is preferably an isothermal reactor, comprising a heat exchanger immersed in the catalyst.
    [018] So, the remodeling process can additionally involve:
    - maintain the existing HTS reactor vessel, replace the high temperature catalyst with a suitable medium temperature catalyst, such as a Cu-Zn catalyst, and provide the vessel with an internal heat exchanger immersed in the catalyst; or
    - install a new medium temperature change reactor (MTS), with an appropriate catalyst and an internal heat exchanger.
    [019] In both of the above options, the heat exchanger is preferably a plate heat exchanger.
    [020] Preferably, a preform section is also added upstream of the primary steam reformer.
    [021] Preferably, the pre-
    reform is also added to amount of primary reformer of steam. [022] From wake up with modalities preferred, the method can understand
    additionally, increasing the oxygen supply to the secondary reformer, through one of the following measures: (a) feeding excess air to said secondary reformer; (b) provide enrichment of the air fed to the secondary reformer; (c) feeding substantially pure oxygen to the secondary reformer. To achieve the above measures, the remodeling process of the
    Petition 870190043784, of 05/09/2019, p. 12/23
    8/13 installation may include the provision that: (a) the existing air fed to the secondary reformer is modified to provide greater air intake; or (b) suitable air enrichment equipment is installed; or (c) an adequate source of substantially pure oxygen is installed, if not available. Said steps may involve the modification or replacement of piping, valves, auxiliary equipment, etc., according to the state of the art.
    [023] In accordance with other additional modalities, additional equipment for purification of the synthesis gas can be installed, in order to provide one of the following actions: cryogenic separation of excess methane and / or nitrogen in the ammonia synthesis gas; separation of excess nitrogen, if any, by an adsorption process, such as PSA; increase of the purge circuit from the synthesis circuit, to provide the removal of inert gases and residual methane.
    [024] As indicated above, an important advantage of the remodeling process of the invention is that, by reducing the proportion of SC in the primary reformer, the overall volumetric flow for a given synthesis gas production is reduced. The volumetric flow is limited by the size of the available equipment, including, for example, the primary reformer tubes, the CO2 removal system, etc. By decreasing the proportion of S / C and then the amount of vapor inert in the gas released by the primary reformer, the method of the invention makes the equipment
    Petition 870190043784, of 05/09/2019, p. 13/23
    9/13 available - originally designed to operate with an S / C ratio close to 3.0 now have a significant margin to increase the flow of useful gas. In other words, the invention makes it possible to reduce the flow rate of vapor substantially inert through the reformers, heat exchangers and other equipment in the installation.
    [025] Thus, for example, reducing the operational proportion of S / C from 3.0 to around 1.5, there will be a theoretical increase of 60% in gas flow. For each mole of methane supplied by the primary reformer, the total flow will be reduced from 4 moles to 2.5 moles. It follows that the capacity of the production plant can be increased by about 60%. In practice, the provision of a new reactor or a modified MTS reactor, while maintaining the other main items of the process steps of the ammonia production plant, can provide a smaller increase, where the primary reformer becomes the bottleneck in terms of maximum flow. Thus, in the example presented above, where the S / C ratio goes from 3.0 to 1.5, the actual production capacity can be increased, typically, by about 25%.
    [026] However, a greater increase in production capacity can be obtained without modifying the internal elements of the primary reformer, if, after the provision of the MTS reactor, instead of the original HTS reactor, one or more of the following measures are taken :
    - provide a greater amount of oxygen to the primary reformer, through
    Petition 870190043784, of 05/09/2019, p. 14/23
    10/13 feeding of excess air or enriched air or pure oxygen, to said primary reformer;
    - improve the purification of the synthesis gas by means of one or more of the techniques listed above, that is, cryogenic separation of excess methane and / or nitrogen in the ammonia synthesis gas; separation of excess nitrogen through adsorption; increased purge of the synthesis circuit.
    [027] Consequently, the remodeling method may include, when necessary, the installation of related equipment, such as air separation unit for enrichment of air or oxygen supply, cryogenic separator, PSA separation section. The method may also include the remodeling of the main synthesis gas compressor, synthesis reactor and other equipment, to process the increased flow of synthesis gas released in the production process steps.
    [028] It should be noted that the flow of synthesis gas released by the remodeled production process steps may contain less nitrogen than required to react with the stoichiometric ratio of 3: 1, for NH3 synthesis. In this case, the lack of nitrogen can be supplied as a separate stream, which is added to the synthesis gas, preferably on the suction or release side of the main synthesis gas compressor. Said nitrogen stream can be generated by means of an air separation unit. Brief Description of the Figures
    Petition 870190043784, of 05/09/2019, p. 15/23
    11/13 [029] Figure 1 represents a flow diagram of the process steps of an ammonia synthesis production plant, according to the invention. Detailed Description of a Preferred Mode [030] With reference to figure 1, a hydrocarbon feed 10, preferably a flow of desulfurized methane, and steam 11 are preheated in a heat exchanger 26 and reacted in a primary reformer 12 and, optionally , pre-reformed in a pre-reformer 12a.
    [031] The supply of natural gas 10 and
    steam 11 is such that the primary reformer 12 is operated with an proportion from steam to carbon bottom The 2, according mentioned above. Per
    For example, feed 11 provides 1.5 moles of steam for every mole of methane in hydrocarbon feed 10.
    [032] A stream of partially reformed gas 13 released by the primary reformer 12 is additionally treated in a secondary reformer 14. An oxidizing agent is supplied through a stream 15 that can provide an excess of air, enriched air or substantially pure oxygen, preferably with a purity greater than 95%, according to several modalities of the invention.
    [033] The gaseous stream 16 from the secondary reformer 14, usually at a temperature around 1000 ° C, is then cooled in a heat exchanger 17 to a temperature of 220 - 320 ° C (stream 18), and sent to a medium temperature change (MTS) reactor 19.
    [034] The MTS reactor is an isothermal catalytic reactor, comprising a bed
    Petition 870190043784, of 05/09/2019, p. 16/23
    12/13 copper based catalyst and a plate-type heat exchanger immersed in the catalytic bed. The entry and exit of a cooling medium is shown by the numerical references 30 and 31.
    [035] Downstream of the MTS 19 reactor, the synthesis gas 20 can later be treated in an optional low temperature change reactor (LTS) 21, to maximize the conversion of carbon monoxide to CO2.
    [036] The synthesis gas is then cooled in a heat exchanger 22 and the cooled synthesis gas stream 23 is sent to treatment steps, usually indicated by block 24, including CO2 removal, methanation and, optionally, purification cryogenic or removal of excess methane through a PSA process. Said cryogenic purification or PSA process can serve to remove unreacted methane in stream 23, caused by the low proportion of S / C in primary reformer 12. Nitrogen (stream 32) can be added, when necessary to achieve the appropriate ratio of H / N for the synthesis of ammonia, in particular, when the oxidizing feed 15 is of highly enriched air or pure oxygen, that is, the nitrogen content in the stream 23 is low. Then, the synthesis gas is compressed and sent to an ammonia synthesis circuit.
    [037] Preferably, all natural gas feed is supplied to the primary reformer; in another embodiment of the invention (not shown), a portion of the raw material for natural gas can be directed to the secondary reformer.
    Petition 870190043784, of 05/09/2019, p. 17/23
    13/13
    Examples [038] A conventional ammonia production plant, with a nominal capacity of 1700 MTD (metric tons per day) of ammonia is remodeled according to the following modalities of the invention:
    a) reduction of the proportion of S / C in the primary reformer to around 1.5 and installation of a pre-reformer, for example, referred to as 12a in figure 1;
    b) the same procedure as (a), with the additional step of providing an excess of air to
    secondary reformer;
    c) the same procedure as (a), with the
    additional step of providing enriched air to the secondary reformer;
    d) the same procedure as (a), with the
    additional step of providing pure oxygen (purity> 95%) to the secondary reformer.
    [039] The production rate can be increased to 2150 MTD (+ 26%) in case (a); for
    2200 MTD (+ 29%) in case (b); to 2500 MTD (+ 47%) in case (c) and 2700 MTD (+ 59%) in case (d). O specific energy consumption (Gcal per BAT),
    including the energy consumed for air separation
    and oxygen production for enrichment air
    case (c)), or for pure oxygen supply case (d)), is reduced by about 0.1 Gcal / BAT in the
    if); about 0.2 Gcal / BAT in the case (B); and
    about 0.5 Gcal / BAT in cases (c) and (d).
    权利要求:
    Claims (4)
    [1]
    1. Process for producing ammonia synthesis gas, from a hydrocarbon-containing raw material, the process comprising the stages of primary reform of the raw material with steam and secondary reform with an oxidizing current, the process being characterized by the fact that :
    - subject the synthesis gas produced by the secondary reform to an average temperature change between 200 and 350 ° C;
    - operate the remodeling primary with an proportion of steam for carbon less than 2.0; - the process comprising a stage in pre-retirement of the raw material cousin, before stage in primary reform. 2. Process, in wake up with The
    claim 1, characterized in that the vapor to carbon ratio is 1.5 to 2, preferably 1.5 to 1.7.
    3. Process according to claim 1 or 2, characterized by selecting the oxidizing current from air, O2-enriched air, or substantially pure oxygen.
    4. Process according to any one of claims 1 to 3, characterized by the fact that it performs the average temperature change in a substantially isothermal condition, by removing heat with a suitable cooling medium.
    5. Process according to any one of claims 1 to 4, characterized in that it additionally comprises the step of removing
    Petition 870190043784, of 05/09/2019, p. 19/23
    [2]
    2/4 unreacted methane from the synthesis gas by means of cryogenic separation of methane from the synthesis gas, or by means of an adsorption treatment step, preferably pressure oscillation adsorption.
    6. Method for remodeling an ammonia plant, comprising a set of process steps for the production of ammonia synthesis gas and a synthesis circuit for reacting the synthesis gas in ammonia, the process steps comprising at least one primary reformer ( 12), a secondary reformer (14), a high temperature change reactor (HTS), the primary reformer being connected to a hydrocarbon supply (10) and a steam supply (11), the method being characterized by the fact that understand at least the steps of:
    - replace the HTS reactor with a new medium temperature change reactor (19), or modify the HTS reactor for operation at medium temperature, the average temperature being 200 to 350 ° C;
    - modify the hydrocarbon supply (10) and steam supply (11) to the primary reformer, in order to obtain the operation of the primary reformer (12) with a vapor to carbon ratio of less than 2;
    - add a section in pre-retirement (12a) upstream of the primary reformer of steam. 7. Method, according with The claim 6, characterized fur fact in understand the modify step The feeding in hydrocarbon s and feeding in steam at the
    Petition 870190043784, of 05/09/2019, p. 20/23
    [3]
    3/4 primary reformer, in order to obtain operation of the primary reformer (12) with a steam to carbon ratio in the range of 1.5 to 2, preferably 1.5 to 1.7.
    8. Method, according to claim 6 or 7, characterized by the fact that it comprises the steps of:
    - maintain the existing HTS reactor vessel, replace the high temperature catalyst with a suitable medium temperature catalyst, such as a Cu-Zn catalyst, and provide the vessel with an internal heat exchanger immersed in the catalyst, or
    - install a new medium temperature change reactor, replacing the existing HTS reactor, the new reactor having a catalyst suitable for operation at medium temperature, and an internal heat exchanger immersed in the catalyst.
    9. Method, of according to any an of claims 6 to 8, featured fur fact in additionally understand any an of following steps: a) modifyThe feeding in air existing to the reformer secondary to provide an
    greater air intake, or
    b) install adequate equipment to enrich the air supply to the secondary reformer, or
    c) install an adequate source of substantially pure oxygen and feed the substantially pure oxygen to the secondary reformer.
    Petition 870190043784, of 05/09/2019, p. 21/23
    [4]
    4/4
    10. Method, according to any an of claims 6 to 9, characterized fur fact in additionally understand any an of following steps:
    - install equipment for the cryogenic separation of excess methane and / or nitrogen in the synthesis gas;
    - install equipment suitable for separation of excess nitrogen in the synthesis gas by an adsorption process, such as a PSA process;
    - increase the purge circuit from the synthesis circuit, in order to remove residual methane.
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    同族专利:
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    CN103879963B|2014-02-20|2015-09-09|康乃尔化学工业股份有限公司|The methanation device of synthetic ammonia optimization production|
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    EP3050849A1|2015-01-27|2016-08-03|Casale SA|A process for the synthesis of ammonia|
    TWI732818B|2016-02-02|2021-07-11|丹麥商托普索公司|A process for producing an ammonia synthesis gas, a process for producing ammonia from such gas, and a plant arranged to carry out such process|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-03-12| B06T| Formal requirements before examination|
    2019-11-05| B09A| Decision: intention to grant|
    2019-12-24| B25A| Requested transfer of rights approved|Owner name: CASALE SA (CH) |
    2020-01-07| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/05/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP10168495.9|2010-07-06|
    EP10168495A|EP2404869A1|2010-07-06|2010-07-06|Process for producing ammonia synthesis gas|
    PCT/EP2011/057729|WO2012004032A1|2010-07-06|2011-05-12|Process for producing ammonia synthesis gas|
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