BRPI0707490A2 - separação de gases leves de halogênios - Google Patents
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Abstract
SEPARAçãO DE GASES LEVES DE HALOGêNIOS. A presente invenção refere-se a um processo que é proporcio- nado para a separação de um ou mais gases leves de bromo ou cloro usan- do uma ou mais separaçoes químicas e contato com um depurador químico para recuperar halogênio adicional. Em um aspecto, o processo compreende (a) fornecimento de uma alimentação de halogênio contendo um ou mais gases leves a uma coluna de destilação ou vaporizador flash; (b) operação da coluna de destilação ou vaporizador flash para separar a alimentação em (i) um primeiro líquido contendo uma quantidade principal de halogênio e não mais do que uma quantidade mínima de gás(es) leve(es) e (ii) um primeiro vapor contendo uma quantidade principal de gás(es) leve(es) e não mais do que uma quantidade mínima de halogênio; e (c) fornecimento do vapor a um depurador químico para recuperar halogênio do vapor.
Description
Relatório Descritivo da Patente de Invenção para "SEPARAÇÃO DE GASES LEVES DE HALOGÊNIOS".
Campo da Invenção
A presente invenção refere-se, de modo geral, a processos paraa separação de gases inertes e outros compostos de halogênio.
Antecedentes da Invenção
A escolha entre ar e oxigênio como um meio para oxidação temsido explorada para muitos usos industriais. Para processos onde ar podeser usado para oxidação sem afetar adversamente a química de reação, ar épreferido com relação a uma alimentação de oxigênio puro em virtude decapital e custo de operação reduzidos. O maior custo do oxigênio resulta dosgastos de separação de oxigênio de nitrogênio, convencionalmente realizadausando membranas ou destilação. Um exemplo onde o uso de oxigênio puroé preferido com relação ao ar é na produção de syngas, a qual é a primeiraetapa na produção de hidrocarbonetos líquidos a partir de gás natural usan-do síntese de Fischer Tropsch. Além de afetar a química de reação, o uso dear na geração de syngas requer que o nitrogênio seja separado do gás natu-ral não convertido. A separação de nitrogênio de gás natural é de custo in-tensivo e é convencionalmente realizada usando membranas ou adsorçãocom modulação de pressão.
Um método convencional de captura de bromo residual em cor-rentes de gás inerte é usar um depurador alcalino, por exemplo, uma solu-ção de NaOH. Não é fácil recuperar o bromo capturado através do métodode depuração convencional. Outros métodos convencionais incluem o usode sulfito de sódio, bissulfito de sódio ou uma solução aquosa de hidróxidode cálcio etc., cada um dos quais sofre da mesma deficiência de que o bro-mo capturado é difícil de recuperar.
A tecnologia desenvolvida pela GRT, Inc., de Santa Barbara,CA, permite que hidrocarbonetos superiores sejam sintetizados a partir demetano ou gás natural através de mistura do(s) hidrogênio(s) e halogênio emum reator para formar haletos de alquila e haleto de hidrogênio, HX. Os hale-tos de alquila e HX são dirigidos em contato com um óxido de metal e halo-gênio, ambos os quais são reciclados. Quando ar é usado para oxidação, ohalogênio que é gerado contém gases inertes, tais como nitrogênio e dióxidode carbono os quais, se não removidos, poderiam passar através da seçãode halogenação e da seção de acoplamento, onde hidrocarbonetos superio-res são produzidos. Em outra tecnologia desenvolvida pela GRT, Inc., hidro-carbonetos são formados através de reação de haletos de alquila com halo-gênio na presença de um catalisador, HX é formado como um subproduto.Para regenerar halogênio para uso em um subseqüente ciclo do processoglobal, HX é oxidado com ar ou oxigênio na presença de um catalisador. Pa-ra ambos os tipos de tecnologias, é desejável separar o halogênio regenera-do de N2, CO2 e outros gases leves (tais como hidrocarbonetos leves nãoreagidos) e água antes que o halogênio seja usado no próximo ciclo de pro-cesso. Para um processo cíclico ou contínuo, tais gases, particularmentenitrogênio, se acumulariam rapidamente se não separados. Existe uma ne-cessidade evidente por um processo eficiente, de custo eficaz, de separaçãode gases inertes e outros compostos de halogênio.
Sumário da Invenção
De acordo com a invenção, é proporcionado um processo paraseparação de um ou mais gases leves de bromo ou cloro usando uma oumais separações físicas e contato com um depurador químico para recupe-rar halogênio adicional. De acordo com um aspecto da invenção, o processocompreende (a) fornecimento de uma corrente de halogênio contendo um oumais gases leves a uma coluna de destilação ou vaporizador flash; (b) ope-ração da coluna de destilação ou vaporizador flash para separar a alimenta-ção em (i) um primeiro líquido contendo uma quantidade principal de halo-gênio e não mais do que uma quantidade mínima de gás(es) leve(s) e (ii) umprimeiro vapor contendo uma quantidade principal de gás(es) leve(s) e nãomais do que uma quantidade mínima de halogênio; e (c) fornecido de vapora um depurador químico para recuperar halogênio do vapor.
Em um segundo aspecto da invenção, duas ou mais separaçõesfísicas são usadas, com cada separação levando a enriquecimento sucessi-vamente maior, respectivamente, do halogênio na fase líquida e do(s)gás(es) leve(es) na fase vapor. Por exemplo, o vapor de uma coluna de des-tilação (enriquecida em gás(es) leve(es)) pode ser alimentado a uma segun-da coluna de destilação, a qual ainda separa o material em um novo vapor eum novo líquido, o novo vapor sendo mais enriquecido em gás(es) leve(es) eo novo líquido sendo mais enriquecido em halogênio.
O depurador químico utilizado na invenção contém um ou maisseqüestrantes de halogênio, materiais os quais são capazes de absorverquimicamente halogênio, em algumas modalidades através de uma reaçãoredox com o halogênio. Um material preferido é brometo de cobre (I) (CuBr,"brometo cuproso"), o qual pode adsorver bromo através de conversão embrometo de cobre (II) (CuBr2, "brometo cúprico").
Breve Descrição dos Desenhos
As características e vantagens da invenção se tornarão melhorcompreendidas quando de consideração à luz da descrição e fazendo refe-rência aos desenhos a seguir, em que:
A figura 1 é um diagrama esquemático de um processo para se-paração de gases leves de bromo de acordo com um aspecto da invenção;
A figura 2 é um diagrama esquemático do processo mostrado nafigura 1, com os elementos adicionais de formação de bromo ("regeneraçãode bromo") e adsorção de água;
A figura 3 é um diagrama esquemático de um processo para se-paração de gás(es) leve(es) de bromo, utilizando três vaporizadores flashoperados em série, de acordo com outro aspecto da invenção;
A figura 4 é um diagrama esquemático de um processo contínuopara conversão de gás natural em hidrocarbonetos superiores e incluindoum subprocesso para separação de bromo formado durante o processo apartir de gases leves, de acordo com um aspecto da invenção;
A figura 5 é uma ilustração esquemática de um método experi-mental de determinação da decomposição de halogênio em um seqüestrantede halogênio usado em uma modalidade da invenção;
A figura 6 é uma fotografia de um tubo de CuBr que foi exposto auma corrente de bromo/nitrogênio, de acordo com um aspecto da invenção.Descrição Detalhada da Invenção
No novo processo da presente invenção, um ou mais gases le-ves são separados de bromo ou cloro através de separação física de umaalimentação do halogênio contendo um ou mais gases leves em um líquido eum vapor, o líquido contendo uma porção principal de halogênio e não maisdo que uma quantidade mínima de gás(es) leve(es) e o vapor contendo umaquantidade principal de gás(es) leve(es) e não mais do que uma quantidademínima de halogênio. Halogênio adicional é removido do vapor passando omesmo através de um depurador químico contendo um seqüestrante de ha-logênio. Conforme usado aqui, um "gás leve" é um tendo um ponto de ebuli-ção menor do que o halogênio como o qual ele está misturado. Os pontos deebulição do bromo e cloro em pressão atmosférica são de aproximadamente59-C e -34-C, respectivamente. Incluídos na definição estão gases tais co-mo nitrogênio (N2)1 dióxido de carbono (CO2) e "hidrocarbonetos leves" - C1-C4 hidrocarbonetos, com a advertência de que C4 hidrocarbonetos (butanose butenos) não são considerados "gases leves" se cloro é o halogênio deinteresse, uma vez que o ponto de ebulição do cloro é menor do que aqueledos C4 hidrocarbonetos. Os termos "quantidade principal" e "quantidade mí-nima" são relativos; um líquido (ou vapor) contém uma quantidade principalde um primeiro componente e uma quantidade mínima de um segundo com-ponente contém mais do primeiro componente do que do segundo compo-nente. Em geral, na maioria das modalidades da invenção, uma determinadafase líquida (ou vapor) consistirá predominantemente de um componente(halogênio ou gás(es) leve(es)), com muito pouco do outro componente.
Uma modalidade da presente invenção é ilustrada na figura 1, aqual representa um sistema 10 para separação de gases leves (nesse caso,nitrogênio e dióxido de carbono) de bromo. Uma alimentação 12 de bromocontendo N2 e CO2 é fornecida a uma coluna de destilação 14 tendo umaparte superior 16 e uma parte inferior 18. Permutadores de calor 20 e 22 a-tuam como condensador parcial e refluxo total, respectivamente, permitindoque um líquido "no fundo" enriquecido em bromo (e contendo não mais doque uma quantidade mínima de gases leves - - tipicamente, não mais do queo limite de solubilidade dos dois gases em bromo) seja extraído da coluna dedestilação, com diminuição adicional da temperatura obtida pelo permutadorde calor 24.
Na parte superior da coluna, refluxo total do líquido do tambor derefluxo é facilitado pelo permutador de calor 22, proporcionando um vaporenriquecido em gases leves (e contendo não mais do que uma quantidademínima de bromo), o qual é enviado a um depurador químico 26, onde aquantidade mínima de bromo é removida, proporcionando um gás leve (pro-dutos nitrogênio e dióxido de carbono). Conforme descrito abaixo, bromopode ser recuperado do depurador através de aquecimento do mesmo.
Em outra modalidade da invenção (não mostrada), duas ou maiscolunas de destilação são conectadas em série, com a parte superior (vapor)de cada coluna sendo enviada como uma alimentação para a próxima colu-na, para enriquecimento de gás leve contínuo do vapor e enriquecimento debromo da corrente "no fundo" de cada coluna.
Para um ambiente de destilação, pressões típicas oscilam de0,01 MPa a 5 MPa (0,1 bar a 50 bar), mais preferivelmente 0,5 a 2MPa (5 a20 bar), com uma temperatura dependente da pressão do sistema de desti-lação, tendo em mente que o ponto de ebulição normal do bromo é de apro-ximadamente 50 EC. O número de estágio pode oscilar de 2 a 200, maispreferivelmente 5 a 30.
A figura 2 ilustra uma variação da modalidade mostrada na figu-ra 2, com a alimentação de halogênio (por exemplo, Br2) vindo de uma uni-dade de regeneração de halogênio 28. Nessa modalidade, a alimentação dehalogênio de 28 contém água, a qual é removida em uma unidade de adsor-ção de água (contendo um dessecante). Alternativamente, a alimentação éprimeiro destilada para remover o bromo da água, até os limites do azeotro-po de bromo-água que se forma, com água residual sendo removida emuma coluna de absorção de água de dessecante.
Em uma modalidade alternativa da invenção, uma ou mais uni-dades de separação flash de vapor-líquido ("vaporizadores flash") são usa-das para separar a alimentação de halogênio e gases leves, seguido porseparação adicional no depurador químico. A figura 3 ilustra um de tais sis-temas 50, no qual uma alimentação de bromo, contendo nitrogênio e dióxidode carbono, é fornecida a um primeiro vaporizador flash 52. Os conteúdosdo vaporizados são Iampejados ("flashed"), proporcionando um primeiro li-quido enriquecido em bromo (por exemplo, recuperação de 97% de Br2) eum primeiro vapor enriquecido em gas leve (N2, CO2) contendo apenas umaquantidade mínima de bromo. O primeiro vapor é alimentado a um segundovaporizador flash e os conteúdos são lampejados, proporcionando um se-gundo líquido enriquecido em bromo (onde, por exemplo, mais 1,5% de Br2são recuperados) e um segundo vapor enriquecido em gás leve, o qual pas-sa através de um segundo permutador de calor 58 e, então, é alimentado aum terceiro vaporizador flash 60. Os conteúdos do terceiro vaporizador flashsão, então, flashed proporcionando, por exemplo, mais 0,5% de Br2 (líquido)e um vapor muito enriquecido em gases leves. A quantidade residual de bro-mo nessa terceira corrente de vapor é removida em um depurador de bromo 62.
Se desejado, vaporizadores flash adicionais podem ser utiliza-dos. Como uma questão prática, contudo, há um ponto de rendimento de-crescente (em termos da quantidade de bromo adicional recuperado) alémdo qual requisitos de capital e custos de operação aumentados provavel-mente não serão justificados.
Sistemas mistos, empregando coluna(s) de destilação e vapori-zadores) flash, podem ser usados.
Em geral, para a separação de gases leves de bromo, cada va-porizador flash é operado em uma temperatura de -60°C a 409C, mais prefe-rivelmente -20°C a 10°C e uma pressão de 0,01 a 5 MPa (0,1 a 50 bar), maispreferivelmente 0,5 a 2 MPa (5 a 20 bar), tendo em mente as diferenças nospontos de ebulição entre o halogênio e o(s) gás(es) leve(es) contido(s). Uma três flashes são preferidos. A pressão pode ser variada nos flashes; contu-do, para reduzir custos, é desejável operar os flashes na pressão de sistemaa fim de evitar compressão, a qual é cara. A temperatura para operação dosflashes é dependente da pressão. Por exemplo, uma operação em alta pres-são pode permitir separação muito boa de bromo mesmo em temperaturasmodestamente altas. Para menores pressões, contudo, um refrigerante podeser necessário para resfriamento das unidades de flash. A série de flashesde vapor-líquido pode consistir em um ou mais flashes.
Um aspecto importante da presente invenção é o método de de-puração química de bromo ou cloro a partir de uma corrente de gás muitodiluída consistindo principalmente em gases leves. O método usa um depu-rador de halogênio capaz de absorver halogênio. De preferência, o seqües-trante absorve vapores de bromo da corrente de gás diluída e, então, podeliberá-lo reversivelmente de volta como bromo livre, quantitativamente. Ad-sorção de bromo pode ocorrer em temperatura ambiente ou temperaturaelevada.
Em geral, qualquer material capaz de reagir com bromo e liberá-lo quando de aquecimento pode ser usado como seqüestrante de bromo.Exemplos não Iimitativos de materiais considerados como sendo adequadospara uso como seqüestrantes de halogênio incluem CuBr, CuC1, FeBr2,FeCI2, AuC1, AuBr, InBr, InCI1 FeO, Cu2O, Hg2Br2, Cu, Ag, Au, Hg, Pt, Pd,Ru, Rh, Fe, Os e Ir, usados sozinhos ou em combinação. No momento, CuBré preferido. Se brometo de cobre com alta área de superfície (sobre um su-porte) é usado, atividade muito maior é observada mesmo embora a quanti-1 dade total de brometo de cobre seja muito menor. Também descobriu-seque CuBr feito através de um processo de precipitação é melhor do que Cu-Br de estoque.
Brometo de cobre (I) reage com bromo para formar brometo decobre (II) de acordo com a seguinte reação: 2CuBr + Br2 2CuBr2. A rea-ção é rápida e completa e, vantajosamente, ocorre em baixas temperaturas.A reação parece ser ligada pela superfície. Quando usando CuBr bruto, a-proximadamente 1% do sólido é usado antes que decomposição ocorra. (Adensidade do CuBr e CuBr2 é muito similar e a superfície não refresca bem;4,6 versus 4,0 g/cm3). Em virtude do fato de a reação de CuBr com vapor deBr2 ser uma reação de um gás com um sólido, a taxa de reação é limitadapela interface sólido-gás e, conseqüentemente, quanto maior a área de su-perfície, maior a reatividade. Na verdade, grandes cristais de CuBr puro sãoo adsorvente menos eficaz. Quando decomposição ocorre (Br2 não é maisretido pelo sólido), a quantidade de CuBr consumido é de aproximadamente0,2% da capacidade total do sólido, o que significa que apenas a superfíciedo sólido participa da reação. A baixa temperatura de reação diminui a pos-sibilidade de migração de íons e o uso do CuBr bruto restante presente.
A capacidade do CuBr de absorver Br2 em baixas temperaturasé vantajosa em parte em virtude do fato de que a corrente de gás inerte(contendo uma quantidade residual de bromo) que vem da separação debromo está em baixa temperatura ou temperaturas ambientes; portanto, ope-ração do depurador em ou próximo das temperaturas ambientes não requerentrada de energia adicional.
O bromo depurado é recuperado através de regeneração do só-lido (nesse caso, brometo de cobre (II)) através de aquecimento do mesmopara acima de 250 QC, tipicamente de 250°C a 275°C. A reação de regene-ração é: 2CuBr2 (calor) 2CuBr + Br2. Onde brometo de cobre é o seqües-trante, a regeneração é termicamente ativada e não requer oxigênio.
O seqüestrante de halogênio pode ser usado como um pó brutoou depositado sobre um suporte. Exemplos não Iimitativos incluem sílica,alumina, zircônia, titânia, WO3, CaO, MgO, Cr2O3 e vários carburetos, nitre-tos e materiais similares. O requisito primário é que o suporte tenha uma á-rea de superfície de 5 a 1500 M2/g. Nos experimentos, usou-se Cu(I)Br sóli-do ou Cu(I)Br depositado sobre Davicat SiZr4700 ou Davicat Si1151A (Da-vidson Corporation), sílicas com alta área de superfície (aproximadamente300 m2/g. SÍ4700B contém -3% em peso de ZrO2. Outros suportes seriamigualmente eficazes na realização da reação de depuração com relação aobrometo de cobre.
O seqüestrante de halogênio ou seqüestrante mais suporte po-dem ser utilizados em uma configuração de reator com coluna empacotadaou outras configurações, tal como um reator com envoltório e tubo. Meios detransferência de calor padrão podem ser usados para distribuir o calor re-querido para manter os ingredientes ativos do depurador na temperatura deregeneração. O esquema de processo pode incluir dois reatores, nos quaisum sofre depuração, enquanto que o outro sofre regeneração.
O agente de depuração sólido é capaz de reter completamentetodo o teor de bromo do fluxo de gás inerte (a perda de bromo do depuradorfoi estimada como sendo menos de 1 ppb). Brometo de cobre (I) suportadomostra resultados reproduzíveis após múltiplos ciclos de exaustão e regene-ração.
Quando um suporte (tal como sílica) é usado, a superfície nãohomogênea gera sítios de nucleação os quais causam a formação de crista-litos menores, com área de superfície apreciavelmente maior. Mesmo onde omaterial suportado contém apenas 15% em peso de CuBr, sua maior áreade superfície de CuBr o torna um melhor material para retenção de vapor debromo.
Para explorar a eficácia do brometo de cobre (I) como um se-qüestrante de halogênio, uma série de experimentos foi conduzida, usandoCuBr comercialmente disponível, CuBr suportado e CuBr formado através deprecipitação. O seqüestrante original (CuBr) foi regenerado através de aque-cimento do CuBr2. Os resultados são apresentados na Tabela 1.
TABELA 1 - RESULTADOS DE REMOVACÁO DE Br2
<table>table see original document page 10</column></row><table>
Notas:
A quantidade % de Br total retida pelo seqüestrante.Regeneração está completa a 275°C dentro de 10-15 min.Vários ciclos foram testados sem diminuição na atividade para CuBr/4700B.
* - traço de AgBr formado, mas o peso medido é <10"4g.
**- após regeneração, sua eficácia diminui com relação àquela do materialcomercial.
A figura 6 é uma fotografia de um tubo de CuBr precipitado ex-posto a uma corrente de bromo/nitrogênio durante trinta minutos em tempe-ratura ambiente. O material escuro de CuBr2. Quando de aquecimento, a correverte para o verde claro do CuBr1 liberando bromo.
Protocolo Experimental: 30 sccm/min. N2 misturado com 1,5sccm de N2 indo através do borbulhador de Br2 esfriado para O0C- O leito deadsorvente sólido estava contido em um tubo de vidro cilíndrico com um di-âmetro de 1 cm. A duração da exposição a tal bromo diluído criado em nitro-gênio foi de 40 minutos em temperatura ambiente. O gás tratado com depu-rador foi borbulhado através de um sifão contendo NaOH a 1M.
Preparo de materiais de CuBr suportado. O suporte foi dis-perso em uma solução a -20% em peso de CuBr2 em água e borbulhadocom SO2 até que a cor da solução se tornasse quase incolor. A suspensãofoi filtrada e seca a 115 eC durante a noite.
Regeneração. A regeneração do bromo retido foi conduzida a-través de aquecimento do reator com o agente de depuração sólido apósexaustão a 275 sC durante 20 minutos. O bromo liberado foi coletado equantificado através de captura do bromo liberado em uma solução sifão deNaOH a 1M. Recuperação quase completa do bromo capturado é possível.
Quantificação. A quantidade de bromo não retido pelo agentede depuração ou regenerada do agente de depuração esgotado foi quantifi-cada através de absorção em um sifão de NaOH o qual, no final, foi acidifi-cado com HNO3 até que o pH caísse para 5 ou abaixo, seguido pela precipi-tação de AgBr usando AgNO3 a 0,5 M em excesso (adicionado até que maisnenhuma precipitação ocorresse). A quantidade do bromo presente foi calcu-lada a partir do ganho de massa de um filtro fritado de vidro usado para filtrare secar o precipitado de AgBr, até que seu peso não mudasse.
A decomposição de bromo é determinada usando uma precipita-ção do Br e BrO" com Ag+, em que o sifão de NaOH é acidificado com HNO3até ácido; AgN03 é adicionado até que mais nenhuma precipitação se for-me; a suspensão foi deixada envelhecer durante 40 minutos, então, filtradasobre um funil fritado de vidro pré-pesado, seco até um peso constante e adiferença de massa é AgBr.
AgNO3 + Br" AgBr9 + NO3"AgNO3 + BrO" AgBr09 + NO3"AgBrO -> AgBr + O2
A constante de solubilidade, Ksp, para AgBr é 5 χ 10"13 mol21"2. Asolução de AgNO3 é 0,5 M - 3 ml (ou mais) adicionada para um total de -20-ml de sifão de NaOH acidificado. A concentração final de Ag+ é ~0,06M.A menor concentração detectável de Br- é~8x 10"12M, o que corresponde a-0,6 ppb. Mesmo se um caso não ideal seja admitido (alta resistência iônica,atividade de íons diferente de 1), a sensibilidade ainda está na faixa de ppb.Exemplo:
Uma corrente de gás inerte de nitrogênio em uma taxa de fluxode 40 sccm (cm cúbico padrão por minuto) contendo aproximadamente 25%de bromo em volume foi tratada de acordo com o método descrito na pre-sente modalidade. A corrente foi esfriada para uma temperatura de 25 -C1 aqual pode ser industrialmente obtida usando um permutador de calor refrige-rado a ar. A corrente, a qual está em uma pressão de 0,25 MPa (25 bar), é,então, Iampejada em uma única unidade de flash de vapor/líquido operandoem uma temperatura de 5 9C. A saída de líquido do flash contém mais de98% do bromo na alimentação original, junto com algum gás inerte que estádissolvido na corrente de bromo. A corrente de vapor contendo o gás inertee bromo residual foi, então, passada sobre um leito de brometo de cobre (I)suportado em temperatura ambiente. A captura de bromo da corrente de gásinerte foi terminada e o leito de depuração realizou captura completa debromo durante um período de 40 min. O leito de depuração esgotado con-tendo brometo de cobre (II) e brometo de cobre (I) foi aquecido para 275 5Ce uma recuperação de bromo quase completa foi observada em um períodode tempo de 15 min.
A invenção encontraria utilidade em um grande número de pro-cessos industriais que usam halogênios como estoques de alimentação ouintermediários para a produção de produtos químicos, onde a recuperaçãoou purificação de halogênio é aperfeiçoada através da remoção de gasesinertes ou leves, resultando em custos de operação e capital significativa-mente reduzidos. Dentre esses, estão os processos para fabricação de álco-ois, éteres, olefinas e alcoxilatos descritos nas Patentes U.S. N- 6.486.368,6.472.572, 6.472.572, 6.465.696, 6.462.243, 6.403.840 e processos para afabricação de hidrocarbonetos superiores, conforme descrito no Pedido dePatente U.S. intitulado "Continuous Process for Converting Hydrocarbon Fo-odstocks into Higher Hydrocarbons and Olefins" (Documento de ProcuraçãoNq 56987/G506) depositado na mesma data em que o mesmo, os conteúdostodos do qual são incorporados aqui por referência. Por exemplo, no proces-so para fazer hidrocarbonetos na faixa da gasolina a partir de gás natural,quando ar é usado para regeneração, o nitrogênio e dióxido de carbono se-guem para a seção de bromação e metátese. Para reciclar metano não con-vertido, separação de nitrogênio de metano é requerida, a qual é de custointensivo. Também, o dióxido de carbono gerado durante a regeneração de-ve ser separado do metano não convertido usando absorção com modula-ção de pressão ou usando um sistema baseado em amina, ambos os quaissão de custo intensivo. A separação de gases leves do bromo não apenasreduz o tamanho do reator, mas também simplifica a separação de gasesleves dos produtos e reagentes não convertidos. O processo de separaçãodescrito aqui oferece uma forma com custo eficaz para separar gases leves(incluindo nitrogênio e dióxido de carbono) de halogênios, tal como bromo.
A invenção foi descrita com várias modalidades e exemplos,mas não está limitada aos mesmos. Outras modificações, bem como equiva-lentes das reivindicações em anexo, estão dentro do escopo da invenção.
Claims (12)
1. Processo para separação de gás(es) leve(es) de bromo oucloro compreendendo:(a) fornecimento de uma alimentação de halogênio contendo umou mais gases leves a uma coluna de destilação ou vaporizador flash;(b) operação da coluna de destilação ou vaporizador flash parseparar a alimentação em gás(es) leve(es) e (ii) um primeiro líquido conten-do uma quantidade principal de halogênio e não mais do que uma quantida-de mínima de gás(es) leve(es) e (ii) um primeiro vapor contendo uma quanti-dade principal de gás(es) leve(es) e não mais do que uma quantidade míni-ma de halogênio; e(c) fornecido do vapor a um depurador químico para recuperarhalogênio do vapor.
2. Processo de acordo com a reivindicação 1, ainda compreen-dendo fornecimento do primeiro líquido a uma coluna de destilação ou vapo-rizador flash para separar o líquido em (i) um segundo líquido contendo umaquantidade principal de halogênio e não mais do que uma quantidade míni-ma de gás(es) leve(es) e (ii) um segundo vapor contendo uma quantidadeprincipal de gás(es) leve(es) e não mais do que uma quantidade mínima dehalogênio; e(c) fornecimento de um segundo vapor a um depurador químicopara recuperar halogênio do vapor.
3. Processo de acordo com a reivindicação 1, em que o halogê-nio é bromo.
4. Processo de acordo com a reivindicação 1, em que o halogê-nio é cloro.
5. Processo de acordo com a reivindicação 1, em que o(s)gás(es) leve(es) compreende(m) nitrogênio.
6. Processo de acordo com a reivindicação 1, em que o(s)gás(es) leve(es) compreende(m) nitrogênio e um ou mais de gases adicio-nais selecionados do grupo consistindo em dióxido de carbono e Ci - C4 hi-drocarbonetos.
7. Processo de acordo com a reivindicação 1, em que o depura-dor químico compreende um leito de um seqüestrante químico suportado ounão suportado.
8. Processo de acordo com a reivindicação 1, em que o seqües-trante de halogênio compreende um material selecionado do grupo consis-tindo em CuBr, CuCI, FeBr2, FeCI2, AuCI, AuBr, InBr, InCI, FeO, Cu2O,Hg2Br2, Cu, Ag, Au, Hg, Pt, Pd, Ru, Rh, Fe, Os, Ir e misturas dos mesmos.
9. Processo de acordo com a reivindicação 1, em que o seqües-trante de halogênio compreende CuBr.
10. Processo de acordo com a reivindicação 1, em que o se-qüestrante de halogênio é suportado sobre um material selecionado do gru-po consistindo em óxidos de metal, carburetos de metal, nitretos de metal,carbono, argila e misturas dos mesmos.
11. Processo de acordo com a reivindicação 1, em que o se-qüestrante de halogênio é suportado sobre um material selecionado do gru-po consistindo em AI2O3, SiO2, ZrO2, TiO2, WO3, CaO1 MgO1 Cr2O1 SiC,Mo4C, TiN, W2N, carbono, zeólito. vermiculita e misturas dos mesmos.
12. Processo de acordo com a reivindicação 1, ainda compreen-dendo aquecimento do depurador químico para liberar halogênio do mesmo.
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JP2009525257A (ja) | 2009-07-09 |
NO20083776L (no) | 2008-11-03 |
CN101395088A (zh) | 2009-03-25 |
EP1993951A4 (en) | 2011-10-19 |
EP1993951B1 (en) | 2014-07-30 |
ZA200807230B (en) | 2009-11-25 |
EA013629B1 (ru) | 2010-06-30 |
WO2007092410A3 (en) | 2007-12-27 |
AU2007212493A1 (en) | 2007-08-16 |
CA2641426C (en) | 2015-06-09 |
EP1993951A2 (en) | 2008-11-26 |
AU2007212493B2 (en) | 2012-09-27 |
MY153701A (en) | 2015-03-13 |
KR101335397B1 (ko) | 2013-12-02 |
WO2007092410A2 (en) | 2007-08-16 |
US7883568B2 (en) | 2011-02-08 |
UA95943C2 (ru) | 2011-09-26 |
ECSP088711A (es) | 2008-11-27 |
EA200870229A1 (ru) | 2009-02-27 |
HK1130758A1 (en) | 2010-01-08 |
SG187456A1 (en) | 2013-02-28 |
CN101395088B (zh) | 2012-04-04 |
KR20080089515A (ko) | 2008-10-06 |
CA2641426A1 (en) | 2007-08-16 |
US20070251382A1 (en) | 2007-11-01 |
JP5275817B2 (ja) | 2013-08-28 |
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