• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
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  • 优先权
    • 专利摘要:
    PROCESS FOR THE COPRODUCTION OF AMMONIA, UREA AND METHANOL. Process for the co-production of ammonia, urea and methanol from natural gas comprising the steps of: (a) production of a synthesis gas by simultaneously feeding natural gas to an autothermal reformer (ATR) and a methane steam reformer (SMR), the two reformers operating in parallel; (b) air supply to an air separation unit (ASU), where the air is divided into oxygen, which is fed to the ATR, and nitrogen; (c) subjecting the synthesis gas from the SMR to a change of gas in water; (d) removing carbon dioxide from the synthesis gas from step (c) and conducting it for urea synthesis in a urea synthesis unit; (e) combining hydrogen-rich gas from step (d) with nitrogen from step (b), removing the catalytic poisons and part of the inert from the gases and conducting the gas mixture for the synthesis of ammonia in an ammonia synthesis unit; (f) optional removal of part of the carbon dioxide from the synthesis gas from ATR (...).
    公开号:BR112015029313B1
    申请号:R112015029313-1
    申请日:2014-04-16
    公开日:2021-02-17
    发明作者:Per Juul Dahl
    申请人:Haldor Topsøe A/S；
    IPC主号:
    专利说明:

    [0001] [0001] The present invention relates to a process for the simultaneous production (co-production) of ammonia, urea and methanol, the said process starting from the production of synthesis gas. More specifically, the underlying idea of the invention is to use a combination of an ATR (autothermal reformer) and a SMR (methane steam reformer) from the front end to obtain the synthesis gas needed for a variety of combinations of ammonia products, urea and methanol.
    [0002] [0002] Autothermal reform is a technology commonly used for the production of synthesis gas, in which the conversion of a hydrocarbon cargo, in this case, natural gas, is carried out in a single reactor, through the combination of partial combustion and reform adiabatic steam. The combustion of the hydrocarbon feed is carried out with sub-stoichiometric amounts of air, oxygen-enriched air or by flame reactions in a combustion zone of the burner. The steam reforming of the partially combusted hydrogen raw material is subsequently carried out in a fixed bed of a steam reforming catalyst.
    [0003] [0003] In the process of steam reforming, synthesis gas is produced from the raw material of hydrocarbon feed through the reactions: CnHm + H2O → nCO + (n + m / 2) H2 (1) CO + H2O → CO2 + H2 (2) CH4 + H2O → CO + 3H2 (3)
    [0004] [0004] The reactions are carried out in an externally heated reactor, the methane steam reformer (SMR), which is a primary reformer. The feed to the primary reformer can be feed of desulfurized hydrocarbons mixed with steam or the gaseous product converted in part, from a previous pre-reform step. The primary reformer is often a tubular firing reformer consisting of tubes filled with catalyst placed in an oven heated by one or more burners. It operates under conditions in which the outlet temperature of tubes filled with catalyst is relatively high, generally in the range of 650 ° C to 950 ° C.
    [0005] [0005] In the autothermal reform the steam reform reactions (1) - (3) are complemented with a partial combustion, which can be represented by the reaction: CH4 + 1/2 O2 → CO + 2H2 (4)
    [0006] [0006] The application WO 2013/013895 A1 published by the applicant describes a flexible process for the production of synthesis gas (syngas) from a hydrocarbon raw material. This process is particularly suitable for large installations of methanol, ammonia and liquid hydrocarbons. The synthesis gas is produced in two stages of steam reforming in simple piping. The process according to the published application can be used for the synthesis of ammonia, methanol, dimethyl ether (DME), liquid hydrocarbons and their combinations.
    [0007] [0007] Various processes for the co-production of ammonia and urea and methanol and ammonia are known. Thus, a process for the combined production of ammonia and urea through the synthesis of carbamate is known from US 2001/0002245 A1, and a method for the simultaneous modernization of a plant for the production of ammonia and a plant for the production of urea , likewise through carbamate synthesis, is known in EP 1 041 038 B1. US 6,448,441 B1 discloses a gasification process for the coproduction of ammonia and urea, in which two parallel gasifiers are used, in order to optimize the H2 / CO2 ratio in the combined synthesis gas product, thereby maximizing the ammonia and urea production.
    [0008] [0008] US 2008/0207948 A1 describes a method for the production of urea from natural gas, in which the natural gas is subjected to partial oxidation or autothermal reform with a gas containing oxygen, in a first stage and the gas The resulting crude synthesis, consisting essentially of CO, CO2, CH4 and H2, can be transformed by catalytic conversion of CO and H2O to form CO2 and H2, after which CO and CH4 are removed in a gas cleaning process. multiple steps and hydrogen is converted to ammonia by adding nitrogen. The ammonia is subsequently recombined with the CO2 previously separated in a second stage, in which the ammonia is completely converted to urea.
    [0009] [0009] A process for the production of ammonia and urea is described in WO 2012/126673 A1, where liquid ammonia produced in an ammonia section is supplied to a urea section directly at the pressure of ammonia synthesis, and in which the liquid ammonia is purified at high pressure by cooling, separation of a gas fraction comprising nitrogen and hydrogen from liquid ammonia cooled to a high pressure and reheating of liquid ammonia, after separation of the gas fraction, thus obtaining an ammonia purified water reheated to a temperature that is suitable for feeding the urea synthesis process.
    [0010] [0010] US 2012/0148472 A1 describes a process for the coproduction of methanol and ammonia, in which a mixture of synthesis gas consisting essentially of carbon monoxide, carbon dioxide and hydrogen is first partially reacted in a reaction reactor single-pass methanol, unreacted synthesis gas is divided into a first and a second stream, the first stream being purified and fed to an ammonia synthesis section, and the second stream being fed to the purification and synthesis section of methanol. The process allows the production of methanol and ammonia in a single integrated process from natural gas and air, and a balanced production of ammonia and carbon dioxide also allows a co-production of urea to be integrated.
    [0011] [0011] Finally, US 2007/0299144 describes a method for co-producing methanol and ammonia from natural gas in a multi-stage process, whereby natural gas, steam and oxygen are mixed in a first reactor, in which the natural gas is partially oxidized and further catalytically reformed. The gas mixture from the first reactor is divided into a stream for the synthesis of methanol and another stream for the production of hydrogen. The CO present in the stream for the production of hydrogen is catalytically converted into CO2 in another reactor with intermediate cooling, and remaining impurities, such as methane, traces of CO and argon being removed. CO2 is branched for urea synthesis. The methanol synthesis gas is catalytically converted to methanol, which is brought to the required purity by distillation, and the ammonia synthesis gas is compressed and catalytically converted to ammonia, which is separated from the synthesis gas recovered by partial condensation.
    [0012] [0012] The aforementioned published application WO 2013/013895 A1 pertaining to the applicant describes a parallel and combined SMR and ATR reform scheme for the preparation of synthesis gas, which can further be converted and / or purified as necessary for the production of hydrogen, carbon monoxide, mixtures of hydrogen and carbon monoxide, as well as for the production of methanol, ammonia, dimethyl ether (DME) and liquid hydrocarbons. The present invention is a further development of the process scheme described in the published application. This invention relates to the integration of nitrogen from an air separation unit (ASU) and CO2 optimization for the co-production of ammonia, urea and methanol.
    [0013] (a) produção de um gás de síntese por alimentação simultânea de gás natural a um reformador autotérmico (ATR) e a um reformador a vapor de metano (SMR), os dois reformadores operando em paralelo; (b) alimentação de ar a uma unidade de separação de ar (ASU) , onde o ar é dividido em oxigênio, o qual é alimentado ao ATR, e nitrogênio; (c) sujeição do gás de síntese a partir do SMR a uma mudança de gás em água; (d) remoção do dióxido de carbono do gás de síntese a partir da etapa (c) e conduzindo o mesmo para a síntese de ureia em uma unidade de síntese de ureia (e) combinação do gás rico em hidrogênio a partir da etapa (d) com o nitrogênio a partir da etapa (b), removendo os venenos catalíticos e parte dos inertes provenientes dos gases e conduzindo a mistura de gás para a síntese de amônia em uma unidade de síntese de amônia; (f) remoção de parte do dióxido de carbono do gás de síntese a partir de ATR na etapa (a) e conduzindo o mesmo para a síntese de ureia em uma unidade de síntese de ureia; e (g) condução do gás de síntese a partir da etapa (f) para a unidade de síntese de metanol; em que o gás de síntese a partir da etapa (a) pode ser conduzido tanto a partir da corrente de saída de ATR para a corrente de saída de SMR a montante do estágio de deslocamento ou para outro caminho.[0013] More specifically, the present invention relates to a process for the co-production of ammonia, urea and methanol from natural gas, which comprises the steps of: (a) production of a synthesis gas by simultaneously feeding natural gas to an autothermal reformer (ATR) and to a methane steam reformer (SMR), the two reformers operating in parallel; (b) air supply to an air separation unit (ASU), where the air is divided into oxygen, which is fed to the ATR, and nitrogen; (c) subjecting the synthesis gas from the SMR to a change of gas in water; (d) removing carbon dioxide from the synthesis gas from step (c) and conducting it for urea synthesis in a urea synthesis unit (e) combining hydrogen-rich gas from step (d) with nitrogen from step (b), removing the catalytic poisons and part of the inert from the gases and conducting the gas mixture for the synthesis of ammonia in an ammonia synthesis unit; (f) removing part of the carbon dioxide from the synthesis gas from the ATR in step (a) and conducting it for the synthesis of urea in a urea synthesis unit; and (g) conducting the synthesis gas from step (f) to the methanol synthesis unit; wherein the synthesis gas from step (a) can be conducted either from the ATR output current to the SMR output current upstream of the displacement stage or to another path.
    [0014] [0014] The combined use of an SMR and an ATR running in parallel makes it possible to produce both ammonia, which can be further converted into urea, and methanol in the same plant, with an optimal use of CO2. Since ammonia, urea and methanol are all desired products, the air separation unit (ASU) is fully utilized, because oxygen goes to the methanol part of the plant, while nitrogen goes to the ammonia part of the plant. . The use of this combination of an ATR and an SMR makes it possible to obtain the synthesis gas necessary for several different combinations of the products of ammonia, urea and methanol. By using an ATR, overall costs can be reduced, and it is even possible to build larger capacity co-production units compared to using only one front end of SMR.
    [0015] [0015] When urea is produced from natural gas through a front-end SMR, this usually leads to a CO2 deficit requiring over-reform. In the process according to the invention, a CO2-deficient gas from the SMR is mixed with a CO2-rich gas from the ATR, which provides a means to optimize the CO2 balance.
    [0016] [0016] The process according to the invention is carried out as illustrated in the attached figure. Natural gas (NG) is fed to each of the two reformers, that is, the autothermal reformer (ATR) and the methane steam reformer (SMR). Simultaneously, the air is fed to an air separation unit (ASU), in which the air is separated into O2, which is conducted to the ATR via pipeline 1, and N2 which is carried forward via pipeline 3 as a source of air. nitrogen for NH3 synthesis. The hydrogen that remains after CO2 removal must be passed, either through a methanator, before being mixed with ASU nitrogen, or a nitrogen wash. In both cases, the resulting mixture of N2 and H2 is sent to the synthesis of NH3 through pipeline 4.
    [0017] [0017] Part of the synthesis gas produced in the ATR is fed through the pipe 5 to a CO2 removal unit and from there to the methanol synthesis. The remainder of said synthesis gas can be passed to inlet displacement through the pipe 2, as shown in the figure, however the passage can also be inverted, that is, from the SMR for the methanol synthesis.
    [0018] [0018] The removal of carbon dioxide from the synthesis gas from step (c) can be carried out by any conventional means in a chemical or physical wash as known in the art. Preferably, the carbon dioxide is removed by any properly known process, which allows for the easy recovery of absorbed carbon dioxide for use in the synthesis of urea.
    [0019] [0019] The carbon dioxide separated from the synthesis gas above is mixed with the carbon dioxide removed after displacement, and the resulting gas is passed through the pipe 6 for the synthesis of urea.
    [0020] [0020] The combination of hydrogen-rich gas from step (d) with nitrogen from step (b) is carried out as an H2 / N2 cleaning, where carbon monoxide is converted into methane, at least a methanation reactor, preferably an adiabatic reactor containing a fixed bed of a methanation catalyst.
    [0021] [0021] The ammonia synthesis gas from the methanisation phase, which contains the correct proportion of hydrogen and nitrogen (3: 1 molar ratio of H2: N2) is optionally passed through a compressor (not shown), the in order to obtain the required ammonia synthesis pressure, such as 120 to 200 bar (12 to 20 MPa), preferably about 130 bar (13 MPa). Ammonia is then produced in a conventional manner, using an ammonia synthesis circuit that comprises at least one ammonia converter containing at least one fixed bed of ammonia catalyst, with cooling between beds. Ammonia can be recovered from the ammonia-containing effluent as liquid ammonia by subsequent condensation and separation. Preferably, a stream of gaseous effluent containing hydrogen, nitrogen and methane is removed from the ammonia synthesis phase, as is also a vapor rich in hydrogen (> 90% by volume of H2). These currents can result, for example, from a purge gas recovery unit.
    [0022] [0022] The required ratio of steam to carbon (S / C ratio), defined as the molar ratio between the total amount of water vapor added to the process in the steam reform step and the carbon contained in the hydrocarbon feed, depends on the specific steam reforming technique. Typical S / C values for synthesis gas preparation are> 0.4 for ATR and> 1.4 for SMR, respectively. When using ATR in the combined plant according to the invention, it is possible to operate with a lower total S / C ratio, which is an advantage, because it allows savings in construction of 10 to 15%. The use of N2 from ASU as a source of N2 for the synthesis of NH3 as mentioned will provide additional construction savings in the gas preparation and cooling sections, since N2 does not pass through them.
    [0023] [0023] In the process according to the present invention, the synthesis gas from the ATR has an S / C ratio between 0.4 and 1.8, and is preferably around 0.6. The SMR synthesis gas has an S / C ratio between 1.4 and 3.3, preferably around 2.5.
    [0024] - Se for necessário mais metanol, gás de síntese do SMR será dirigido para a síntese de metanol. - Se for necessária mais ureia, gás de síntese do ATR será dirigido para o deslocamento à jusante do ATR e CO2 será opcionalmente removido a partir da alimentação do gás de síntese para a síntese de metanol e usado para a produção de ureia. [0024] The invention allows optimal CO2 management for full production of methanol and urea product combinations. - If more methanol is needed, SMR synthesis gas will be directed to methanol synthesis. - If more urea is needed, ATR synthesis gas will be directed to the downstream displacement of the ATR and CO2 will be optionally removed from the synthesis gas feed for methanol synthesis and used for the production of urea.
    [0025] [0025] The invention can also be used to produce liquid ammonia in combination with methanol and urea. In this case, the invention will help to reduce or even in some cases avoid excess CO2 from the process.
    [0026] [0026] The invention is described in more detail in the following example with reference to the figure, which illustrates the concept of the invention. EXAMPLE
    [0027] [0027] The conditions for an ATR reform section and an SMR reform section are listed in Table 1. Pure methane is used as the feed in the example, but it can be any typical hydrocarbon feed. The result for a natural gas containing higher hydrocarbons and / or CO2 will lead to a relatively larger SMR section compared to the ATR section used in the example.
    [0028] [0028] Table 1 below shows the composition of the dry gas in the synthesis gases, the consumption of oxygen and the available nitrogen.
    [0029] [0029] The dry gas compositions show the difference in the composition of carbon and hydrogen making it possible to optimize CO2 management, such that the total process can be carried out without excess CO2.
    [0030] [0030] It is evident that, even if all the synthesis gas is used to obtain urea, there will be an excess of nitrogen.
    [0031] [0031] In Table 2 below, the results of various product scenarios are calculated. A characteristic common to all cases is that all the CO2 in the process is used to produce urea and / or methanol. The table shows that the concept allows any division of the product between urea and methanol, without excess CO2 from the process.
    *) MTPD = metric tons per day
    权利要求:
    Claims (7)
    [0001]
    Process for the co-production of ammonia, urea and methanol from natural gas, characterized by the fact that it comprises the steps of: (a) production of a synthesis gas by simultaneously feeding natural gas to an autothermal reformer (ATR) and to a methane steam reformer (SMR), the two reformers operating in parallel; (b) air supply to an air separation unit (ASU), where the air is divided into oxygen, which is fed to the ATR, and nitrogen; (c) subjecting the synthesis gas from the SMR to a change of gas in water; (d) removing carbon dioxide from the synthesis gas from step (c) and conducting it for urea synthesis in a urea synthesis unit (e) combining hydrogen-rich gas from step (d) with nitrogen from step (b), removing the catalytic poisons and part of the inert from the gases and conducting the gas mixture for the synthesis of ammonia in an ammonia synthesis unit; (f) removing part of the carbon dioxide from the synthesis gas from the ATR in step (a) and conducting it for the synthesis of urea in a urea synthesis unit; and (g) conducting the synthesis gas from step (f) to the methanol synthesis unit; wherein the synthesis gas from step (a) can be conducted either from the ATR output stream to the SMR output stream upstream of the displacement stage or to another path.
    [0002]
    Process according to claim 1, characterized by the fact that the synthesis gas from ATR has a vapor to carbon ratio (S / C ratio) between 0.4 and 1.8, preferably around 0, 6.
    [0003]
    Process according to claim 1, characterized by the fact that the synthesis gas from the SMR has an S / C ratio between 1.4 and 3.3, preferably around 2.5.
    [0004]
    Process according to claim 1, characterized by the fact that the synthesis gas from the SMR is sent to the methanol synthesis unit to increase methanol production.
    [0005]
    Process according to claim 1, characterized in that the synthesis gas from the ATR is sent to the displacement downstream of the ATR and CO2 is optionally removed from the synthesis gas supply to the methanol synthesis unit to increase urea production.
    [0006]
    Process according to claim 1, characterized in that the SMR synthesis gas is directed to the synthesis of methanol, if a higher proportion of methanol is desired.
    [0007]
    Process according to claim 1, characterized by the fact that the synthesis gas is directed to the downstream displacement to the ATR and CO2 is optionally removed from the synthesis gas supply for the synthesis of methanol and used for the production of urea, if a higher proportion of urea is desired.
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    法律状态:
    2019-11-05| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-12-08| B09A| Decision: intention to grant|
    2021-02-17| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 16/04/2014, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    EP13168896.2|2013-05-23|
    EP13168896.2A|EP2805914B1|2013-05-23|2013-05-23|A process for co-production of ammonia, urea and methanol|
    PCT/EP2014/057765|WO2014187621A1|2013-05-23|2014-04-16|A process for co-production of ammonia, urea and methanol|
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