TW200811086A - Process for preparing 2-hydroxy-4-(methylthio)butyronitrile and methionine - Google Patents
Process for preparing 2-hydroxy-4-(methylthio)butyronitrile and methionine Download PDFInfo
- Publication number
- TW200811086A TW200811086A TW96125214A TW96125214A TW200811086A TW 200811086 A TW200811086 A TW 200811086A TW 96125214 A TW96125214 A TW 96125214A TW 96125214 A TW96125214 A TW 96125214A TW 200811086 A TW200811086 A TW 200811086A
- Authority
- TW
- Taiwan
- Prior art keywords
- acrolein
- carried out
- methionine
- ammonia
- reaction
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/18—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by addition of thiols to unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
- C07C319/20—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
Abstract
Description
200811086 九、發明說明： 【發明所屬之技術領域】 本發明之領域係有關由丙烯醛製備2-羥基_4_(甲硫基) 丁腈（後文稱之為HMTBN)作為中間產物或作為終產物。本 5 發明之領域亦係有關由HMTBN製備2-胺基-4-(甲硫基)丁酸 (後文稱作甲硫胺酸）。最後，本發明之領域為由丙稀酸製備 甲硫胺酸。 【ilyr 】 此等化合物之化學式如下 丙埽醛 ΗΜΤΒΝ 10200811086 IX. Description of the invention: [Technical field to which the invention pertains] The field of the invention relates to the preparation of 2-hydroxy-4-(methylthio)butyronitrile (hereinafter referred to as HMTBN) from acrolein as an intermediate product or as an end product . The field of the invention of this invention is also related to the preparation of 2-amino-4-(methylthio)butyric acid (hereinafter referred to as methionine) from HMTBN. Finally, the field of the invention is the preparation of methionine from acrylic acid. [ilyr] The chemical formula of these compounds is as follows: Propionaldehyde ΗΜΤΒΝ 10
QHQH
甲硫胺酸 大致上，於一第一步驟中，ΗΜΤΒΝ之合成實作經由丙 烯醛與甲硫醇反應來合成3_(甲硫基）丙醛（或稱作為 ΜΤΡΑ)。於第二步驟巾，如此所得·τρΑ與氫級接觸， 如此獲得ΗΜΤΒΝ。ΜΤΡΑ根據搭所衍生之產物，因此要求 特殊儲存條件。ΜΤΡΑ實際上為極為不穩定之產物，當與空 氣中的氧氣接觸時極為快速分解。此外，通常須儲存於冷 處，因而運送期間造成缺點。 15 200811086 本七月之目的係尋找涉&MTPA中間物之丽丁顺之 合成之替代之道。 本發明之另-個目的係避免儲存不穩定之中間產物或 由於有毒或由於可燃而料造成安全問題之中間產物。 、於HMTBN合成後，通常需要多個反應步驟來獲得甲硫 細夂特％甲硫胺酸之製法要求合成甲硫胺酸乙内酿脈。 :硫胺酸的製備涉及甲硫胺酸乙内醯脲的皂化，亦即與氫Methionine In general, in a first step, the synthesis of hydrazine is carried out by reacting acrolein with methyl mercaptan to synthesize 3-(methylthio)propanal (or as hydrazine). In the second step, the thus obtained τρΑ is brought into contact with the hydrogen level, thus obtaining ruthenium. ΜΤΡΑAccording to the products derived from the plant, special storage conditions are required. Tantalum is actually a highly unstable product that decomposes very rapidly when in contact with oxygen in the air. In addition, it is usually stored in a cold place, thus causing shortcomings during transportation. 15 200811086 The purpose of this July is to find an alternative to the synthesis of Li Dingshun, which involves & MTPA intermediates. Another object of the present invention is to avoid the storage of unstable intermediates or intermediates that are toxic or cause safety problems due to flammability. After the synthesis of HMTBN, it is usually required to obtain a plurality of reaction steps to obtain methyl thiocyanate. The method for producing methyl methionine requires synthesis of intramethyl methionine. : Preparation of thiline involves saponification of carbendazim thiourea, ie with hydrogen
10 1510 15
乳化鈉或絲化鉀水解，因而造成共同產生相當大量納鹽 (例如硫酸鈉）難以探勘之缺點。 山 卜已知藉'氨水解甲硫胺酸乙内醯脲，產生二氧化 石反’ -乳化碳必須由製程中移除或回收。 X月之另一項目的包含由丙烯醛或由ΗΜΤβΝ製造 甲硫胺酸而極少成夫丘 ，、 次禾/、冋產生鹽。「極少」一詞表示每當量 斤形成之甲硫胺酸係低於0.5當量鹽。 本^明之另一目的係無需移除反應共同產物。 為止未冒說明任何方法可由丙烯醛直接進入甲硫 文而無需分離中間產物。 *月之另一目的係提供一種由丙烯醛製備甲硫胺酸 而無需分離中間產物之方法。 對於起^月之又另一目的係提供一種於各個反應步驟，相 、大始物料丙烯醛或11]^11^1^可獲得高產率之方法。 b本發明方法有多項優點。於後文說明過程將出現 更為多項如。 6 200811086 【日月1^3 2 首先，本發明提示一種製備HMTBN之新穎方法，該方 法涉及與先前技術不同之中間產物，亦即2_羥基_3_丁烯腈 (後文稱作為丙烯醛氰醇），該中間產物較為安定。 5 一種由丙烯醛製備2-羥基-4-(甲硫基）丁腈（HMTBN)之 水溶液而未分離中間產物之方法，其特徵在於： -於一第一步驟中，以氫氰酸/丙烯腈之莫耳比1至1〇 進行丙烯醛(2)與氫氰酸(4)間之反應（1)， -於一第二步驟中，以甲硫醇/丙烯醛之莫耳比1至1〇 10 添加曱硫醇(MSH)(63)， 該方法係於pH 3至pH 9進行。 如此由丙烯醛合成HMTBN涉及兩個分開反應步驟。該 二反應步驟表示如下：Emulsified sodium or potassium telluride hydrolyzes, thus causing the disadvantage of co-produced a considerable amount of nano-salt (e.g., sodium sulfate) that is difficult to explore. It is known that the ammonia hydrolysis of thiomethionine and the production of the dioxide anti-emulsion carbon must be removed or recovered from the process. Another item of X month consists of producing a methionine from acrolein or from ΗΜΤβΝ, and rarely forming a sulphur, and producing a salt. The term "very few" means that the amount of methionine formed per equivalent kilogram is less than 0.5 equivalent of salt. Another object of the present invention is to eliminate the need to remove reaction co-products. It has not been stated that any method can directly enter the methyl sulfonate from acrolein without isolating the intermediate product. Another purpose of the month is to provide a method for preparing methionine from acrolein without separating the intermediate product. Still another object for the month is to provide a method for obtaining a high yield in each reaction step, phase, acrolein or 11]^11^1^. b The method of the invention has several advantages. In the following description, the process will appear more numerous. 6 200811086 [Sun and Moon 1^3 2 First, the present invention proposes a novel method for preparing HMTBN, which involves an intermediate product different from the prior art, that is, 2-hydroxy-3-butenenitrile (hereinafter referred to as acrolein). Cyanohydrin), the intermediate product is relatively stable. 5 A process for preparing an aqueous solution of 2-hydroxy-4-(methylthio)butyronitrile (HMTBN) from acrolein without separating the intermediate product, characterized in that: - in a first step, hydrocyanic acid / propylene The reaction of acrolein (2) with hydrocyanic acid (4) is carried out at a molar ratio of nitrile to 1 to 1 Torr, in a second step, with a molar ratio of methyl mercaptan / acrolein 1 to 1〇10 Add hydrazine thiol (MSH) (63), which is carried out at pH 3 to pH 9. Thus synthesizing HMTBN from acrolein involves two separate reaction steps. The two reaction steps are expressed as follows:
丙烯醛氰醇Acryl cyanohydrin
HMTBN 7 200811086 但皆未曾有先前技術文件說明由丙烯醛合成ΗΜΤΒΝ 而未分離中間產物。 本發明也提示一種由Η Μ T B N製備甲硫胺酸之新穎方 法。該方法之起點為ΗΜΤΒΝ，其特徵在於未分離中間產 5 物·，氨及二氧化碳添加至ΗΜΤΒΝ之水溶液，又獲得至少包 含甲硫胺酸、一氧化碳及氮呈溶解形式之混合物。 由ΗΜΤΒΝ連續製備甲硫胺酸之方法，根據該方法進行 包含該ΗΜΤΒΝ之水溶液(2)之氨水解⑴，該方法之特徵在 於： 10 ⑷始於NHVHMTBN之莫耳比為5至50，以及始於 CCVHMTBN之莫耳比為1至1〇，於不超過25〇。〇之溫度，於 水相連續進行ΗΜΤΒΝ之氨水解反應⑴，此反應係連續進行 且未分離中間產物，因而獲得包含至少甲硫胺酸、二氧化 碳及氨呈溶解形式之輸出混合物（5)及ΗΜΤΒΝ衍生之產 15 物；以及 (b)該ΗΜΤΒΝ衍生之產物、二氧化碳及氨循環至水解 ⑻。 最後，本發明提示一種製備甲硫胺酸之新穎方法。該 方法之起點為丙稀酸，並未分離中間產物，該方法之特徵 20 在於： -於一第一步驟中，進行丙烯醛與氫氰酸間之反應， -於一第二步驟中，甲硫醇(MSH)添加至該第一步驟之 反應混合物， 該二步驟係於pH 3至pH 9間進行， 8 200811086 又獲得HMTBN之水溶液。 -於一第三步驟中，氨及二氧化碳添加至ΗΜΤΒΝ水溶 液， 轉而獲得包含至少甲硫胺酸、二氧化碳及氨呈溶解形 5 式之混合物。 「未分離中間產物」之表示法意圖表示於ΗΜΤΒΝ或甲 硫胺酸之製造過程中未曾分離中間產物。實際上，如前文 說明，由丙烯醛製備ΗΜΤΒΝ及曱硫胺酸之方法涉及兩個共 通反應步驟。其中一個反應步驟特別製造丙烯醛氰醇。根 10據本發明舉例言之，此種中間產物未被分離，亦即未經萃 取或經傾析。換言之，水解反應為「單一容器式」反應。 根據本發明，未經中間產物之分離或分選進行該方法。 根據本發明方法之「單一容器式」實作於該等方法於 工業規模製造時可提供相當特殊的優點。 15 ΗΜΤΒΝ之製法 根據本發明之製備ΗΜΤΒΝ之方法係利用兩個連續反 應進行，第一反應涉及添加氫氰酸(HCN)至丙烯醛之羰基， 因而獲得丙晞酸氰醇；及第二反應涉及添加曱硫醇(後文稱 作為MSH)至丙烯酸氰醇。此二反應步驟係於pH 3至pH 9間 20 進行。 根據本發明之一個實施例，於第一步驟中，以氫氰酸/ 丙埽駿之莫耳比為1至1〇較佳為1至3進行丙烯駿與氫氰酸 間之反應。 此外，根據本發明之另一個實施例，於第二步驟中， 9 200811086 MSH係以MSH/丙烯醛之莫耳比為峨佳為丨至3添加。 此二步驟之反應溫度為10°c至12(TC。較佳反應溫度為 60°C 至 l〇〇°c。 根據本發明HMTBN之製法之前二步驟之主要特徵之 5 一為控制進行此等反應之PH。大致上本發明之反應係於pH 3至pH 9且較佳為於pH 4至pH 8進行。 熟諳技藝人士瞭解如何調節反應介質之pH。舉例言 之，可使用緩衝液。根據本發明，「緩衝液」一詞意圖表示 具有pH 3至pH 9，由弱酸與強鹼或由強酸與弱鹼所組成之 10任一種溶液。舉例言之，特別為擰檬酸緩衝液、碳酸緩衝 液及麟酸緩衝液。 根據本發明之特佳實施例，一種緩衝溶液用於整個處 理程序。單一緩衝液的使用可簡化處理程序的實作。實際 上可充分修改溶液之pH來獲得期望產物。無需改變緩衝液 15 類型，或無需進行中間純化步驟。 根據本發明之一個實施例，第一步驟係於pH 4至pH 6 間進行，及/或第二步驟係於pH 6至pH 8間進行。 鱼HMTBN製備甲硫胺酸之方法 根據本發明由HMTBN製備甲硫胺酸之方法包含一單 20 一步驟，其中氨及二氧化碳係添加至HMTBN，如此獲得包 含甲硫胺酸之混合物。 於此處理程序結束時所得混合物主要含有曱硫胺酸。 混合物也包含呈溶解形式之二氧化破及氨。 根據本發明之一個實施例，所得送出混合物之二氧化 200811086 碳及氨循環至處理程序的起點，來讓其可再度用於該製程。 根據本發明方法處理期間之反應溫度不超過25〇艽。 此外，根據本發明之一個實施例，該方法係未使用催 化劑，例如未使用固體催化劑，例如未使用金屬氧化物類 5型之固體催化劑進行。 「催化劑」一詞意圖表示於水解反應中未被耗用之任 何化5物，g反應結束時該催化劑可完全再度獲得。於定 義上’催化劑與反應物間並無化學計算學關係。根據本發 明之個Μ施例’該方法係於無催化劑存在下進行，就工 10業上而言，如此可提供相當大優點。 、由ΗΜΤΒΝ製備甲硫胺酸之方法涉及多個反應步驟。此 等多個反應步驟相對於每一莫耳所製造的甲硫胺酸，製造i 莫耳氨及1莫耳二氧化碳。因該方法之進行方式為所製造的 氣及所1^的—氧化碳係循環利用，為了可再用於該方 法，所製造的氨及二氧化碳之莫耳數與所耗用的莫耳數間 形成平衡，讓此等化合物雖然並未出現於反應的整個平衡 表單中’但此等化合物也不可被視為催化劑。 根據本發明，由HMTBN製備甲硫胺酸之方法之天然循 環為較佳。該循環也可利用額外化學處理或酶催化處理來 20 進行。 舉例5之，循環可藉均質催化以化學方式進行，例如 使用水I*生氨水解來以化學方式進行，或藉非均質催化來以 化學方式進行。化學處理可為驗性處理或使用石灰處理。 NH3、NaOH、K0H、Et⑽a、Me〇Na、及K2C〇3構成根據 11 200811086 本發明可使用之鹼之實例。 化學處理也可為使用反向合成催化劑處理。於催化劑 中以固體催化劑例如Ti02或Zr02為佳。 循環也可以酶催化方式例如透過醯胺酶之酶催化方式 5 進行。 全部於文件WO 00/27809所述之甲硫胺酸胺基醯胺水 解之全部路徑皆係適用於本循環。 根據本發明之一個實施例，於該方法結束時，輸出混 合物之壓力減低，然後減壓輸出混合物分離成甲硫胺酸豐 10富之液體流及氨及二氧化碳豐富之氣體流。 於本發明之另一個實施例中，甲硫胺酸豐富之液體流 分離成固體甲硫胺酸其經過抽真空；及甲硫胺酸被耗盡之 水性母液，可能包含衍生產物，於再度將壓力調整回之後， 水性母液循環至製程的起點。 15 於另一個實施例中，水性母液係於化學處理或酶催化 處理後循環。 於另一個實施例中，水性母液自然循環至製程的起點 而未經化學處理或酶催化處理。 根據另一個實施例，甲硫胺酸豐富之液體流係藉逐步 2〇結晶分離，因而獲得固體甲硫胺酸及水性母液。 根據另一個實施例，於冷凝後，氨及二氧化碳豐富流 經儲存，且於壓力被調整回之後循環至製程的起點。 根據本發明之一個實施例，根據該方法之水解係於由 20QC逐步升高至22〇。〇之溫度進行。 12 200811086 根據另一個實施例，根據該方法之水解係於5巴至100 巴之壓力下進行。 根據本發明之一個實施例，該製程係於管狀反應器或 多個串聯的經攪動的反應器内進行。 5 Φ而蝉醛製備甲硫胺酸之方法 根據本發明由丙細备製備甲硫胺酸之方法可利用三個 連續步驟進行，第一步驟涉及添加氫氰酸(HCN)至丙烯酸之 罗炭基，因而獲付丙浠蠢亂醇，笫一步驟涉及添加甲硫醇(後 文稱作為MSH)至丙烯醛氰醇，此二反應步驟係於pH 3至pH 10 9間進行；第三步驟涉及添加氨及二氧化碳至HMTBN。 根據本發明之一個實施例，於第一步驟中，反應係以 氫氣酸/丙細酸莫耳比為1至10而於丙稀酸與氫氰酸間進 行0 根據本發明之另一個實施例，於第二步驟中，MSH係 15以MSH/丙烯醛莫耳比為1至10之比例添加。 根據本發明之另一個實施例，於第三步驟中，始於氨/ 丙烯盤莫耳比為5至50，以及始於二氧化碳/丙烯駿莫耳比 為至20氨及二氧化碳添加至HMTBN之水溶液。 此一步驟之反應溫度為l〇°C至12(TC及/或第三步驟之 20溫度係不超過250°C。 此外，根據本發明之一個實施例，該方法可未使用催 化劑進行。 石山根據本發明之一個實施例，所得送出混合物之二氧化 $二循環至第二步驟，來允許將二氧化碳及氨再度用 13 200811086 於該方法。 根據本發明之一個實施例，於第三步驟後，輸出混合 之壓力降低，減壓輸出混合物被分離成甲硫胺酸豐富之 液體流’及氨及二氧化碳豐富之氣體流。 5 、於本發明之另一個實施例中，甲硫胺酸豐富之液體流 被分離成固體甲硫胺酸經抽真空，及曱硫胺酸被耗盡之水 f母液，可能包含衍生產物，於壓力已經再度調整回第三 步驟時’水性母液被循環至第三步驟。 於另一個實施例中，水性母液係於化學處理或酶催化 10處理後循環利用。 ;另個實施例中，水性母液係未經化學處理或酶催 化處理，自然循環至第三步驟。 姓曰根據另一實施例，甲硫胺酸豐富之液體流係藉階段式 結晶分離，因而獲得固體甲硫胺酸及水性母液。 15 _根據另一個實施例，於冷凝後，氨及二氧化碳豐富流 、工儲存’且於壓力被再度機回之後循#至該製程的起點。 根據本發明之一個實施例，根據該製程之第三步驟之 水解係於溫度以梯階式由坑升高至22代範圍之溫度進 行。 根據另個實施例，根據該方法之第三步驟之水解係 於5巴至100巴間之壓力進行。 根據本务明之一個實施例，該方法之第三步驟係於一 管狀反應器或於多個串聯設置的管狀反應器中進行。 根據本兔明’起始丙烯酸包括視為麵之製法以及 14 200811086 視為甲硫胺酸之製法，丙稀路可呈純質形式，或可利用通 常包含丙埽氧化步驟及/或丙烧氧化步驟之習知方法獲得。 當丙烯醛係經由丙烯之部分氧化製備時，獲得以丙烯 醛為主之粗產物。此種粗產物係呈包含丙烯醛、惰性氣體、 5丙稀、丙烷、水、及反應副產物諸如酸類、醛類、醇類及 其它化合物之氣態混合物形式。 根據本發明之一個實施例，丙烯醛係源自於於水存在 下藉空氣氧化丙稀。此反應經控制，表示部分丙婦並未反 應而維持於所合成之丙烯搭中。大為較佳係循環尚未反應 10 之起始產物。 " 先前技術之HMTBN之製法可免除殘餘丙烯之循環利 用，原因在於後者已經於處理程序期間與含硫產物接觸。 本發明之優點為，本發明允許於丙烯醛合成期間尚未反應 之兩烯作為起始產物之丙烯循環利用。 15 根據本發明之一個實施例，丙烯循環至丙烯醛合成反 應為係於根據本發明由丙烯醛製或製備甲硫胺 夂之方法之第一步驟期間，一旦丙烯醛已經接觸氫氰酸時 進行回收利用。 —根據本發明之一個實施例，丙烯之回收係於丙烯醛或 °氫氰酸之反應性吸收後之氧化進行。 根據本發明之一個實施例，於水存在下丙烯藉空氣氧 化後，而於反應性吸收前，氧化後所得產物中所含的 藉洗滌去除。 ' 以丙烯醛作為起始產物之相同方式，氫氱酸可以純質 15 200811086 形式使用，或氫氰酸可利用氨氧化法獲得，亦即於空氣及 固體催化劑存在下，由甲烷及氨合成氫氰酸。於此種情況 下，源自於合成反應器之氫氰酸之隨後處理為可能。 根據本發明之一個實施例，氫氰酸係於空氣及固體催 5 化劑存在下，由甲烧與氨合成。 根據本發明之一個實施例，於氫氰酸合成後而於反應 吸收前進行洗滌。HMTBN 7 200811086 However, none of the prior art documents describe the synthesis of hydrazine from acrolein without the separation of intermediates. The present invention also suggests a novel process for the preparation of methionine from Η Μ T B N . The starting point of the process is hydrazine, characterized in that the intermediate product is not separated, ammonia and carbon dioxide are added to the aqueous solution of hydrazine, and a mixture containing at least methionine, carbon monoxide and nitrogen in dissolved form is obtained. According to the method for continuously preparing methionine, ammonia hydrolysis (1) containing the aqueous solution (2) of the hydrazine is carried out according to the method, and the method is characterized in that: 10 (4) the molar ratio starting from NHVHMTBN is 5 to 50, and The molar ratio of CCVHMTBN is 1 to 1 〇, and no more than 25 〇. The temperature of the crucible is continuously subjected to an ammonia hydrolysis reaction (1) in the aqueous phase, and the reaction is continuously carried out without separating the intermediate product, thereby obtaining an output mixture (5) containing at least methionine, carbon dioxide and ammonia in a dissolved form. Derived product 15; and (b) the product derived from the hydrazine, carbon dioxide and ammonia are recycled to the hydrolysis (8). Finally, the present invention suggests a novel process for the preparation of methionine. The starting point of the process is acrylic acid, and the intermediate product is not separated. The method 20 is characterized in that: - in a first step, a reaction between acrolein and hydrocyanic acid is carried out, - in a second step, A mercaptan (MSH) is added to the reaction mixture of the first step, which is carried out between pH 3 and pH 9, and 8 200811086 is again obtained as an aqueous solution of HMTBN. - In a third step, ammonia and carbon dioxide are added to the aqueous solution, and a mixture comprising at least methionine, carbon dioxide and ammonia in a dissolved form is obtained. The notation of "unseparated intermediate product" is intended to mean that the intermediate product has not been separated during the manufacture of hydrazine or methionine. In fact, as explained above, the process for preparing hydrazine and hydrazine thioacetate from acrolein involves two common reaction steps. One of the reaction steps specifically produces acrolein. Root 10 According to the invention, such intermediates are not separated, i.e., are not extracted or decanted. In other words, the hydrolysis reaction is a "single container" reaction. According to the invention, the process is carried out without separation or sorting of intermediates. The "single container type" of the method according to the invention provides considerable special advantages in the manufacture of such processes on an industrial scale. Process for preparing ruthenium according to the present invention is carried out by two consecutive reactions involving the addition of hydrocyanic acid (HCN) to the carbonyl group of acrolein, thereby obtaining cyanohydrin; and the second reaction involves A thiol (hereinafter referred to as MSH) is added to the cyanohydrin. The two reaction steps are carried out between pH 3 and pH 9 of 20. According to an embodiment of the present invention, in the first step, the reaction between the acrylonitrile and the hydrocyanic acid is carried out at a molar ratio of hydrocyanic acid / propylidene to 1 to 1 Torr, preferably 1 to 3. Further, according to another embodiment of the present invention, in the second step, 9 200811086 MSH is added with a molar ratio of MSH/acrolein to 33. The reaction temperature of the two steps is from 10 ° C to 12 (TC. Preferably, the reaction temperature is from 60 ° C to 10 ° C. According to the main features of the two steps before the preparation of the HMTBN according to the present invention, the control is carried out. The pH of the reaction. The reaction of the present invention is generally carried out at pH 3 to pH 9 and preferably at pH 4 to pH 8. The skilled artisan knows how to adjust the pH of the reaction medium. For example, a buffer can be used. In the present invention, the term "buffer" is intended to mean any solution having a pH of from 3 to pH 9, consisting of a weak acid and a strong base or consisting of a strong acid and a weak base. For example, particularly a citric acid buffer, carbonic acid Buffer and linonic acid buffer. According to a particularly preferred embodiment of the invention, a buffer solution is used throughout the processing procedure. The use of a single buffer simplifies the handling of the processing procedure. In fact, the pH of the solution can be substantially modified to achieve the desired Product. There is no need to change the type of buffer 15 or an intermediate purification step is required. According to one embodiment of the invention, the first step is carried out between pH 4 and pH 6, and/or the second step is carried out at pH 6 to pH 8. Carry out. Fish HMTBN Process for the preparation of methionine The process for the preparation of methionine from HMTBN according to the invention comprises a single 20 step in which ammonia and carbon dioxide are added to HMTBN, thus obtaining a mixture comprising methionine. The resulting mixture mainly contains guanidine thioglycol. The mixture also contains oxidized oxidized ammonia in dissolved form. According to one embodiment of the present invention, the resulting mixture of oxidized 200811086 carbon and ammonia is recycled to the beginning of the treatment process to allow It can be reused in the process. The reaction temperature during the treatment according to the method of the invention does not exceed 25 〇艽. Furthermore, according to one embodiment of the invention, the process is not using a catalyst, for example without using a solid catalyst, for example without using metal The solid catalyst of the oxide type 5 is carried out. The term "catalyst" is intended to mean any compound which is not consumed in the hydrolysis reaction, and the catalyst can be completely re-obtained at the end of the reaction. By definition, 'catalyst and reactants There is no stoichiometric relationship. According to one embodiment of the present invention, the method is based on the absence of a catalyst. This can provide considerable advantages in terms of the industry. The method for preparing methionine involves a plurality of reaction steps. The plurality of reaction steps are relative to each of the moles produced. Thiamine, which produces i-mole ammonia and 1 mol of carbon dioxide. This method is carried out by recycling the produced gas and the carbon-oxide system, and the ammonia produced for reuse in the process. And the molar number of carbon dioxide and the number of moles consumed are balanced so that these compounds do not appear in the entire equilibrium form of the reaction 'but such compounds are not considered to be catalysts. According to the invention, The natural circulation of the HMTBN process for the preparation of methionine is preferred. The cycle can also be carried out using additional chemical or enzymatic treatments20. For example, the cycle can be carried out chemically by homogeneous catalysis, for example chemically using water I* ammonia hydrolysis or chemically by heterogeneous catalysis. The chemical treatment can be an analytical treatment or a treatment with lime. NH3, NaOH, K0H, Et(10)a, Me〇Na, and K2C〇3 constitute an example of a base which can be used according to the invention of 11 200811086. Chemical treatment can also be carried out using a reverse synthesis catalyst. A solid catalyst such as TiO 2 or Zr 02 is preferred in the catalyst. The cycle can also be carried out by enzymatic means, for example by enzymatic catalysis of a guanamine enzyme. All pathways for the hydrolysis of methionine amine amide as described in document WO 00/27809 are applicable to this cycle. According to one embodiment of the invention, at the end of the process, the pressure of the output mixture is reduced, and then the reduced pressure output mixture is separated into a methionine rich liquid stream and an ammonia and carbon dioxide rich gas stream. In another embodiment of the present invention, the methionine-rich liquid stream is separated into solid methionine which is evacuated; and the methionine depleted aqueous mother liquor may contain derivative products, again After the pressure is adjusted back, the aqueous mother liquor is recycled to the starting point of the process. In another embodiment, the aqueous mother liquor is recycled after chemical or enzymatic treatment. In another embodiment, the aqueous mother liquor is naturally recycled to the starting point of the process without chemical treatment or enzymatic treatment. According to another embodiment, the methionine-rich liquid stream is separated by gradual 2 crystallization, thereby obtaining solid methionine and an aqueous mother liquor. According to another embodiment, after condensation, ammonia and carbon dioxide are enriched for storage and are recycled to the beginning of the process after the pressure is adjusted back. According to one embodiment of the invention, the hydrolysis according to the method is gradually increased from 20QC to 22〇. The temperature of the crucible is carried out. 12 200811086 According to another embodiment, the hydrolysis according to the process is carried out at a pressure of from 5 bar to 100 bar. According to one embodiment of the invention, the process is carried out in a tubular reactor or a plurality of stirred reactors in series. 5 Φ and decalaldehyde to prepare methionine method According to the invention, the method for preparing methionine from propylene can be carried out in three successive steps, the first step involves the addition of hydrocyanic acid (HCN) to acrylic charcoal Base, thus obtaining a propanol, a step involving the addition of methyl mercaptan (hereinafter referred to as MSH) to acrolein, the two reaction steps are carried out between pH 3 and pH 10; It involves the addition of ammonia and carbon dioxide to HMTBN. According to an embodiment of the present invention, in the first step, the reaction is carried out with a hydrogen acid/propionic acid molar ratio of 1 to 10 and between acrylic acid and hydrocyanic acid. According to another embodiment of the present invention In the second step, the MSH system 15 is added in a ratio of MSH/acrolein molar ratio of from 1 to 10. According to another embodiment of the present invention, in the third step, the ammonia/propylene disk molar ratio is from 5 to 50, and the carbon dioxide/propylene molar ratio is from 20 ammonia and carbon dioxide is added to the aqueous solution of HMTBN. . The reaction temperature of this step is from 10 ° C to 12 (TC and/or the temperature of the third step of 20 does not exceed 250 ° C. Further, according to an embodiment of the present invention, the method can be carried out without using a catalyst. According to one embodiment of the invention, the resulting mixture is oxidized by two dioxins to a second step to allow carbon dioxide and ammonia to be reused in the process at 13 200811086. According to one embodiment of the invention, after the third step, The pressure at the output mixing is reduced, and the reduced pressure output mixture is separated into a methionine-rich liquid stream' and an ammonia and carbon dioxide-rich gas stream. 5. In another embodiment of the invention, the methionine-rich liquid The stream is separated into solid methionine by vacuuming, and the thiol acid depleted water f mother liquor may contain derivative products. When the pressure has been adjusted back to the third step, the aqueous mother liquor is recycled to the third step. In another embodiment, the aqueous mother liquor is recycled after chemical treatment or enzymatic catalysis 10 treatment. In another embodiment, the aqueous mother liquor is not chemically treated or enzymatically catalyzed. According to another embodiment, the methionine-rich liquid stream is separated by stage crystallization, thereby obtaining solid methionine and an aqueous mother liquor. 15_ According to another embodiment After condensation, ammonia and carbon dioxide enrich the flow, work storage 'and after the pressure is re-machined back to # to the starting point of the process. According to one embodiment of the invention, the hydrolysis according to the third step of the process is based on temperature According to another embodiment, the hydrolysis according to the third step of the method is carried out at a pressure between 5 and 100 bar. According to one embodiment of the present invention The third step of the method is carried out in a tubular reactor or in a plurality of tubular reactors arranged in series. According to the invention, the starting acrylic acid comprises a method of forming a surface and 14 200811086 is regarded as methionine. In the process, the propylene path may be in a pure form, or may be obtained by a conventional method generally comprising a propylene oxide oxidation step and/or a propylene oxidation step. When the acrolein is partially oxidized by propylene, Obtaining a crude product mainly composed of acrolein. The crude product is a gaseous mixture containing acrolein, an inert gas, 5 propylene, propane, water, and reaction by-products such as acids, aldehydes, alcohols and other compounds. According to one embodiment of the present invention, acrolein is derived from the oxidation of propylene by air in the presence of water. This reaction is controlled to indicate that some of the propylene is not reacted but is maintained in the synthesized propylene. It is preferred to recycle the starting product that has not yet reacted to 10. " The prior art process of HMTBN eliminates the recycling of residual propylene because the latter has been contacted with the sulfur-containing product during the processing. Advantages of the Invention The propylene which is allowed to react as a starting product during the acrolein synthesis is recycled as a starting product. 15 According to one embodiment of the present invention, the propylene is recycled to the acrolein synthesis reaction to produce or produce methyl sulfide from acrolein according to the present invention. During the first step of the amine oxime process, the acrolein is recycled once it has been exposed to hydrocyanic acid. - According to one embodiment of the invention, the recovery of propylene is carried out by oxidation after reactive absorption of acrolein or ° hydrocyanic acid. According to an embodiment of the present invention, the propylene is oxidized by air in the presence of water, and the oxidized product contained in the product is removed by washing before the reactive absorption. 'In the same way as acrolein as the starting product, hydroquinone can be used in the form of pure 15 200811086, or hydrocyanic acid can be obtained by ammoxidation, ie hydrogen synthesis from methane and ammonia in the presence of air and solid catalyst Cyanate. In this case, subsequent treatment of hydrocyanic acid originating from the synthesis reactor is possible. According to one embodiment of the present invention, hydrocyanic acid is synthesized from a methane and ammonia in the presence of air and a solid catalyst. According to one embodiment of the invention, the washing is carried out after the synthesis of hydrocyanic acid and prior to the absorption of the reaction.
類似地，曱硫醇可以純質形式或粗產物形式用於本發 明方法。也可於甲醇、硫化氫及固體催化劑存在下源自於 10 合成。 本發明方法所使用之反應器特別為管狀反應器、攪拌 反應器或批次式反應器。 HMTBN也可為2·羥基冰（甲硫基）丁酸(HMTB A)合成 中之中間產物。 15 因此本發明也係關於製備HMTBA之方法，包含如前文 定義之製備HMTBN之方法及一步驟包含獲得hmtBA。 第1至14圖以非限制性方式表示製備液之裝 置或由HMTBN或由丙烯醛製備甲硫胺酸之裝置。 圖式簡單說明 20 第卜2及3圖以非限制性方式表示根據本發明由丙烯酸 製備HMTBN之溶液之三個裝置。 第4至6圖顯示第3圖製備HMTBN之裝置之某些部分。 第7及8圖示意顯示根據本發明*HMTBN製備甲硫胺 酸之兩種裝置。 16 200811086 第9及10圖示意顯示根據本發明由HMtbn製備甲硫胺 酸之裝置之其它實施例。 第11至14圖示意顯示根據本發明由丙烯醛製備甲硫胺 酸之四種裝置。 5 方式】 較佳實施例之詳細說明 第1圖顯示一種製備HMTBN之溶液之裝置，包含兩個 管狀反應器1及60。該方法之第一步驟，亦即由丙烯醛及氫 氰酸合成丙烯醛氰醇係於管狀反應器〗中進行；本發明方法 1〇之第二步驟，亦即將甲硫醇添加至第一步驟所得之丙烯醛 氰醇係於管狀反應器60進行。 雖然第1圖顯示兩個管狀反應器，但根據本發明全然可 能包含於一個經攪拌之反應器或批次式反應器内進行本發 明方法。 15 管狀反應器1於2被進給丙烯醛，及於3被進給氫氰酸。 氫氰酸/丙稀醛之莫耳比為1至10且較佳為1至3。 也於4提供期望用於調節pH之進料，如前文說明為本發 明之主要特徵。 pH調節溶液例如緩衝溶液係於其它進料流3與2混合後 20 被導入。 氫氰酸係呈約20%至80%重量比之水溶液形式。此溶液 可於裝置外側製備，但也可提供線上導入水。 丙烯醛氰醇61係於反應器輪出1回收，隨後被送至管狀 反應器60。 17 200811086 管狀反應器60也於63被進給甲硫醇。也於64被提供期 望用於調節pH之進料。 HMTBN水溶液係於62回收。 第2圖顯示一種製備HMTBN之溶液之裝置，包含兩個 5 $狀反應态1及60。該方法之第一步驟，亦即由丙浠駿及氣 氰酸合成丙烯醛氰醇係於管狀反應器1中進行；本發明方法 之第二步驟，亦即將甲硫醇添加至第一步驟所得之丙烯醛 氰醇係於管狀反應器60進行。 管狀反應器1於2被進給丙烯醛，及於3被進給氫氰酸。 10氫氰酸/丙烯醛之莫耳比為1至10且較佳為1至3。 也於4提供期望用於調節pH之進料，如前文說明為本發 明之主要特徵。Similarly, hydrazine thiol can be used in the process of the present invention in pure form or in crude form. It can also be derived from the synthesis in the presence of methanol, hydrogen sulfide and a solid catalyst. The reactor used in the process of the invention is in particular a tubular reactor, a stirred reactor or a batch reactor. HMTBN can also be an intermediate in the synthesis of 2 hydroxy ice (methylthio)butyric acid (HMTB A). The invention therefore also relates to a process for the preparation of HMTBA comprising a process for the preparation of HMTBN as defined above and a step comprising obtaining hmtBA. Figures 1 through 14 show, in a non-limiting manner, a device for preparing a preparation or a device for preparing methionine from HMTBN or from acrolein. BRIEF DESCRIPTION OF THE DRAWINGS 20 Figures 2 and 3 show, in a non-limiting manner, three devices for preparing a solution of HMTBN from acrylic acid in accordance with the present invention. Figures 4 through 6 show some parts of the apparatus for preparing HMTBN in Figure 3. Figures 7 and 8 show schematically two apparatus for the preparation of methionine according to the invention *HMTBN. 16 200811086 Figures 9 and 10 show schematically other examples of apparatus for preparing methionine from HMtbn in accordance with the present invention. Figures 11 through 14 schematically illustrate four apparatus for the preparation of methionine from acrolein in accordance with the present invention. 5 Modes] Detailed Description of the Preferred Embodiments Fig. 1 shows a device for preparing a solution of HMTBN comprising two tubular reactors 1 and 60. The first step of the method, that is, the synthesis of acrolein by acrolein and hydrocyanic acid is carried out in a tubular reactor; the second step of the method of the present invention, that is, the addition of methyl mercaptan to the first step The obtained acrolein is carried out in a tubular reactor 60. Although Figure 1 shows two tubular reactors, it is entirely possible according to the invention to carry out the process of the invention in a stirred reactor or batch reactor. 15 The tubular reactor 1 is fed with acrolein at 2 and hydrocyanic acid at 3. The molar ratio of hydrocyanic acid to acrylaldehyde is from 1 to 10 and preferably from 1 to 3. The feed desired to adjust the pH is also provided at 4, as previously described for the main features of the present invention. A pH adjusting solution such as a buffer solution is introduced after mixing the other feed streams 3 and 2. The hydrocyanic acid is in the form of an aqueous solution of from about 20% to about 80% by weight. This solution can be prepared on the outside of the device, but it is also possible to provide water on the line. Acryl cyanohydrin 61 is recovered in reactor 1 and subsequently sent to tubular reactor 60. 17 200811086 Tubular reactor 60 is also fed with methyl mercaptan at 63. Also available at 64 is expected to be used to adjust the pH of the feed. The HMTBN aqueous solution was recovered at 62. Figure 2 shows a device for preparing a solution of HMTBN comprising two reaction states 1 and 60. The first step of the method, that is, the synthesis of acrolein from the cyanide and the cyanuric acid is carried out in the tubular reactor 1; the second step of the method of the invention also adds the methyl mercaptan to the first step. The acrolein is carried out in a tubular reactor 60. The tubular reactor 1 is fed with acrolein at 2 and hydrocyanic acid at 3. The molar ratio of 10 hydrocyanic acid / acrolein is from 1 to 10 and preferably from 1 to 3. The feed desired to adjust the pH is also provided at 4, as previously described for the main features of the present invention.
被導入。 15 氫氰酸係呈約20%至80%重量比之水溶液形式。此溶液 可於裝置外側製備，但也可提供線上導入水。 於管狀反應器1之後有一管柱15其可循環氫氰酸氣 相。此種管柱也可調整導入管狀反應器1之氫氰酸數量。 丙烯醛氰醇61係於反應器輸出1回收，隨後被送至管狀 20反應器60。 管狀反應器60也於63被進給甲硫醇。也於64被提供期 望用於調節pH之進料。 於管狀反應器6 0之後有一管柱6 5其可循環甲硫醇氣 相。此種管柱也可調整導入管狀反應器60之曱硫醇數量。 18 200811086 HMTBN水溶液係於62回收。 現在參照第3圖及第4、5及6圖說明ΗΜΤΒΝ之製法。 該方法係實作第一反應步驟，於根據第3圖之情況下， 其為第一反應性吸收1。第一反應性吸收1被進給包含丙歸 5 醛之氣態流2。也被進給包含氫氰酸之氣態流3。 反應介質流係於吸收管柱1中循環。pH特別可透過進料 至此反應介質流之進料4來調節。 如第4圖之詳細說明，包含丙烯醛之氣態流2係源自於 氧化20，接著為洗滌25。 10 氧化反應器20被進給丙烯21、空氣22及水23。其為氣 相丙烯氧化反應器。 粗產物24於反應器輸出產生。此粗產物24包含一種氣 態混合物，其包含難以冷凝之高重量百分比氣體（丙烷、氮 氣、氧氣、丙烯、一氧化碳、二氧化碳）、水、丙烯醛、丙 15 烯酸及其它化合物。 如此，根據本發明之一個實施例，涵蓋於水23存在下， 使用空氣22氧化20丙烯21後而於反應性吸收1之前，藉洗滌 25移除氧化後所得產物中所含之酸。 因此此粗產物24進行洗滌25，允許其移除酸。呈氣體 20 24形式之粗產物被導入洗滌管柱25，水流26及水流27於洗 滌管柱25中循環。水26挾帶酸。含酸之液體27係於洗滌管 柱25底部萃取。純化後之氣體2於管柱25頂部送出，且被導 引至反應性吸收1。 如第5圖之詳細說明，反應性吸收1也被進給包含氫氰 19 200811086 酸之氣態流3 ° 此氣態流3係源自於合成反應器3〇，接著為洗滌^。 合成反應器30被進給氨31、甲烷32及空氣幻。涉及例 如於空氣及固體催化劑存在下，使用氨對甲烷進行氨氧 5 化。反應極為快速。於極高溫進行。 於反應器輸出30製造富含氫氰酸之粗產物34。 於冷卻後，此粗產物34係於反應器輸出30獲得，然後 於反應性吸收1之前進行洗滌35。尚未反應之氨係利用於管 柱頂部36被導入之硫酸水溶液而被移除，硫酸水溶液係於 10洗滌管柱35中於逆流方向循環。於管柱35底部37萃取硫酸 銨。 如第6圖詳細說明，於吸收裝置〗於其中進行根據本發 明之HMTBN合成之第一步驟，於吸收裝置丨頂部所得氣熊 出物可於洗務管柱50部分循環，反應介質51流係循環於 15洗滌管柱50中。裝置52允許由其它較輕質的化合物（c〇、 C〇2、氮氣、Η2及HCN)中分離丙烯。例如該裝置可為吸收 於水之裝置或壓縮與冷卻裝置。氫氰酸係以水洗滌（吸收） 被移除；丙烯係藉冷凝及蒸餾回收，或丙烯係於有機溶劑 藉吸收回收因此可與無法冷凝之產物（二氧化碳、一氧化 2〇 碳、氮氣等）分離。 過里丙細未被污染（原因在於過量丙烯並未與含硫產 物接觸）因此可被循環利用，此點係與先前技術方法相反， 先前技術方法涉及丙烯醛與甲硫醇接觸。如前文說明，此 乃本發明之技術優勢。 20 200811086 如此循環之丙烯隨後被導引至進料管21，進料管進給 至氧化反應器20，透過管子幻製造丙烯醛。 如此，根據本發明之一個實施例，丙稀之循環53係於 反應性吸收1之後至氧化20之前進行。 5 洗滌管柱50之底部係利用管54被導引至蒸餾管柱55。 循％利用的氫S文係於療顧管柱55頂部萃取，且經管路％ 被導引至吸收管柱1。 根據第3圖，吸收管柱〗之底餾分其中含有丙烯醛氰醇 係利用進料管61而被導引至第二吸收管柱6〇。 10 於被導入第二管柱之前，可設置一pH測量裝置65。此 裝置65允許調整吸收管柱1中之pH值。 若有所需，於導入管柱6〇前，亦即於第二步驟開始前 可設置管柱1底餾分之儲存槽66。 其中進行該方法之第二步驟之吸收管柱6 〇係以經純化 15之液體或氣體形式被進給含有甲硫醇之氣態流63。 以類似吸收管柱1之方式，反應介質循環通過吸收管柱 60。特別可透過進給至吸收管柱之反應性介質流上之進料 64來調節pfj。 HMTBN水溶液62係於吸收管柱60底部萃取。可設置此 2〇 溶液之儲存裝置。 第7圖表示由包含HMTBN之工業用水溶液ιοί製備甲 硫胺酸之裝置。 該方法係實作連續水相水解70。根據前文定義，此水 解之進行並未單離或分離中間產物。 21 200811086 反應器70被進給水溶液101係利用進料管進行。 於導入反應器70之前，含水性氨及二氧化碳之水相77 經由進料管而被導入包含HMTBN之水溶液101，水溶液1〇1 之壓力事先已經透過幫浦72而被調整回復原先壓力。 5 HMTBN水溶液具有較佳大於30%之濃度。例如可使用 大於或等於60%濃度之HMTBN溶液。溶液也包含水及相關 聯之衍生產物，主要係源自於HMTBN之合成例如源自於氯 氰酸及硫酸。 根據本發明，本合成係使用HMTBN水溶液進行，藉此 10提供多項工業優點。特別，使用HMTBN水溶液可避免使用 汽提管柱(或水蒸氣蒸餾管柱）來回收溶劑。此外就成本及處 理上具有優勢。 根據本發明’當固定溫度時’加諸壓力來具有液相。 反應器70中之溫度係以梯階方式於混合物溫度（亦即2〇〇c 15至90°c間）升高至250°C。根據本發明之較佳實施例，合成 係於20 C至220 C之溫度進行。為了於水相操作，壓力須為 5巴至100巴（較佳約20巴）。 於反應期間，反應斋内溫度係由混合物溫度（亦即 至90°C間）升高至高原期溫度。 20 於反應益70之輸入端’ HMTBN/NH3莫耳比為1/5至1/50 間，例如約1 /20，隨後隨著水性氨相對於hmtbn之大為莫 耳過量。HMTBN/C〇2之莫耳比為！至1/2〇，例如於反應器 70之輸入端約為1/10或1/3。 主要包含甲硫胺酸、二氧化碳及氨呈溶解形式之水溶 22 200811086 液於73回收。 第8圖表示由包含HMTBN之工業用水溶液1〇1製備甲 硫胺酸之裝置。 反應器70被進給水溶液101係利用進料管進行。 5 於導入反應器7〇之前，含水性氨及二氧化碳之水相77 經由進料管而被導入包含HMTBN之水溶液101，水溶液1〇ι 之壓力事先已經透過幫浦72而被調整回復原先壓力。 HMTBN水溶液具有較佳大於30%之濃度。例如可使用 大於或等於60%濃度之HMTBN溶液。溶液也包含水及相關 10 聯之衍生產物，主要係源自於HMTBN之合成例如源自於氫 氰酸及硫酸。 根據本發明，本合成係使用HMTBN水溶液進行，藉此 提供多項工業優點。特別，使用HMTBN水溶液可避免使用 汽提管柱（或水蒸氣蒸餾管柱）來回收溶劑。此外就成本及處 15 理上具有優勢。 根據本發明，當固定溫度時，加諸壓力來具有液相。 反應為70中之溫度係以梯階方式於混合物溫度（亦即2〇。〇 至90 C間）升南至250°C。根據本發明之較佳實施例，合成 係於20 C至220°C之溫度進行。為了於水相操作，壓力須為 20 5巴至100巴（較佳約2〇巴）。 於反應期間，反應器内溫度係由混合物溫度（亦即2〇〇c 至90 C間）升高至高原期溫度。 於反應益70之輸入端，hmtbn/NH3莫耳比為仍至1/5〇 間，例如約1/20 ;隨後隨著水性氨相對於HMTBN2大為莫 23 200811086 5 耳過量。HMTBN/C〇2之莫耳比為1至1/20，例如於反應器 70之輸入端約為1/10或1/3。 主要包含甲硫胺酸、二氧化碳及氨呈溶解形式之輸出 混合物73係於反應器70之出口藉HMTBN之水解獲得。 此混合物於被導入汽提管柱80(也稱作為水蒸氣蒸德 管柱)前，例如利用減壓閥74而被降低壓力例如降低至大氣 壓。 於管柱80中，被導入的減壓混合物分離成為富含甲硫 胺酸之液體流82及富含氨及二氧化碳之氣態流81。 10 於管柱80的頂端，富含氨及二氧化碳也包含水及氣態 流被冷凝成液流83。然後液流83儲存於84。儲存槽84視需 要包含一排氣口 85。 根據本發明，「氨」一詞意圖表示實質含有NH3之相；「水 相氨」一詞意圖表示實質含有NH4OH之相。 15 m 同理，’當述及「含二氧化碳之氣相」時，意圖表示實 質含有氣悲形式之一氧化碳之相；而當述及「含二氧化碳 之水相」時，意圖表示實質含有h2co3之相。 「實質上」一詞表示感興趣之相包含過量所考慮之化 合物，該過量係大於50%，更特別係大於70%。 20 含有水性氣及一氧化奴之水相7 7於其壓力已經再度調 整回復76之後，利用進料管77而被循環至水解反應器7〇。 根據本發明，於壓力被再度調整回之前，也可設置一 進料管75，該進料管75進給氨、二氧化碳及/或水至進料管 77。若有所需，此種進料管允許調整氨、二氧化碳及/或水 24 200811086 含量。 畐含甲硫胺酸之液體流，亦即被Γ酸化」亦即pH降低 之甲硫胺酸水溶液利用撤流管82而於汽提管柱80的底部撤 出。 5 此液體流於熱交換器86中冷卻，可沉澱甲硫胺酸。但 任何其它熟諳技藝人士已知之手段包括蒸發也可於任一點 施用。 如此所得液體被送至分離器90，因此允許由HMTBN所 少亍生之未反應產物留在水相中（稱作為水性母液）中分離呈 1〇 固體形式之甲硫胺酸。 呈固體形式之甲硫胺酸係於95回收，水性母液92係於 壓力已經利用幫浦91調整回之後，經由進料管92送至反廡 器70。此種循環回路為特佳。 第9圖顯示根據本發明之另一種循環可能。 15 於92之曱硫胺酸產生性產物可於循環前進行化學處理 或酶催化處理。甲硫胺酸產生性產物可循環至水解反應器 70 ’循環至汽提管柱8〇或循環至撤流管。 根據本發明之一個實施例，水性母液92係於化學處理 或酶催化處理後循環利用。循環可例如進行至管柱8〇或進 2〇 行至液流82。 根據本發日狀-個實_，水性母㈣未經化學處理 或酶催化處理自然被循環至反應器70。 如第1〇圖所示，根據本發明之一個實施例，甲硫胺酸 之合成係於一管狀反應器或於串聯設置之多個經攪拌之反 25 200811086 應器710、720、730及740中進行。 經攪拌之反應器數目並無特殊限制。較佳係大於3，但 袁大數目並無限制。 根據本發明之一個實施例，富含甲硫胺酸之液流82係 5藉分段結晶91分離，因此首先獲得固體甲硫胺酸95，其次 獲得水性母液92。 分段結晶91也產生含水及輕質產物稱作為「濃縮產物」 之氣態流92。於冷凝93之後，液流94視需要可儲存。 第11圖顯示由丙烯盤製備甲硫胺酸之裝置。HMTBN溶 10 液之製備包含兩個管狀反應器1及6。該方法之第一步驟， 亦即由丙烯醛及氫氰酸合成丙烯醛氰醇係於管狀反應器i 中進行；而本發明方法之第二步驟，亦即添加MSH至第一 步驟所得丙烯醛氰醇係於反應器6進行。 雖然第11圖顯示兩個管狀形式之反應器，但根據本發 15明，也可涵蓋此等步驟係於攪拌反應器或批次式反應器或 任何其它適當反應器内進行。 管狀反應器1於2被進給丙烯酸，以及於3被進給氫氰 酸。氫氰酸/丙烯醛之莫耳比為1至1〇且較佳為1至3。 意圖調節pH之進料也可於4提供，且構成本發明之主要 2〇 特徵。 根據本發明之一個實施例，pH調節溶液例如缓衝溶液 係於其它液流、2及3混合後被導入。 氫氰酸係呈水溶液例如約5%至90%重量比水溶液之形 式被導入。此溶液可於裝置外侧製備，但也可提供水之線 26 200811086 5 上導入。 丙稀酸氰醇61係於反應器1之輸出回收，然後送至管狀 反應器60。 管狀反應器60也於63被進給MSH。也於64被提供意圖 調節pH之進料。 於62回收HMTBN水溶液。 • 該方法也實作一第三步驟70。於導入反應器7〇之前， 透過進料管77添加含有水性氨及二氧化碳之水相至包含 HMTBN之水溶液62。 10 含有HMTBN、水性氨及二氧化碳之水溶液於72壓力被 調整回之後被導入反應器70内。 於反應器70之輸出回收包含甲硫胺酸、二氧化碳及氨 呈溶解形式之混合物73。 15 • 現在將參考第12圖及第13圖說明由丙烯醛製備甲硫胺 酸之方法。此二圖與第11圖之差異在於所顯示之實作方法。 以類似第11圖之裝置，根據第12圖或第13圖製備 HMTBN溶液涉及兩個反應器1及6〇。該方法之第一步驟係 於管狀反應器1中進行，本發明方法之第二步驟係於反應器 60進行。 20 於反應器1之後有個管柱15 ,於其中進送丙稀酸氰醇， 且允許氫氰酸氣相的循環。此種管柱也可調整導入反應器1 中之氫氰酸數量。 丙烯醛氰醇61係於管柱15之輸出回收，然後送至管狀 反應器60。 27 200811086 同理，HMTBN係於反應器60之輸出送至管柱65。如此 可循環利用未反應之產物。 第13圖之裝置與第12圖之裝置之差異在於載明第三步 驟。 含有水性氨及二氧化碳之水相77添加至包含ΗΜΤΒΝ 之水溶液62。整個混合物之壓力利用幫浦72而調整回原先 壓力。 反應器70也被進給水溶液71，亦即主要包含甲硫胺酸 乙内醯脲之工業用溶液，但也包含與甲硫胺酸的產生相關 10 聯之衍生產物，亦即脲基乙酸、脲醯丁醯胺及2-胺基_本（甲 硫基）丁醯胺(也稱作為ΑΜΒΤΜ)。 「甲硫胺酸產生性」一詞意圖表示可藉氨水解來製造 甲硫胺酸之任一種化合物。根據本發明，本身為甲硫胺酸 產生性化合物之乙内醯脲水溶液也包含甲硫胺酸產生性衍 15 生產物，特別為上示脲基乙酸、脲醯丁醯胺及2-胺基·4_(甲 硫基）丁醯胺。就定義上，甲硫胺酸不含括於甲硫胺酸產生 性化合物。 於反應器70的輸出獲得主要包含甲硫胺酸、二氧化碳 及氨之呈溶解形式之輸出產物。 20 於管柱8〇中，被導入之減壓混合物分離成富含甲硫胺 酸之液體流82及富含氨及二氧化碳之氣態流81。 於管柱80之頂端，富含氨及二氧化碳也包含水之氣態 流81被冷凝，然後於84被儲存。儲存槽84視需要可包含一 排氣口 85。 28 200811086 氨氣體部分經冷凝。含水性氨及二氧化碳之水相於壓 力調整回76之後被循環至反應器。 如此，根據本發明之一個實施例，於冷凝後，富含氣 及二氧化碳之液流81被儲存84，且於壓力被調整回76之後 5 循環至第三步驟。 根據本發明也可設置一進料管75，其係於壓力被調整 回之前，進給氨及/或二氧化碳。若有所需，此種進料管也 允許調整氨含量及/或二氧化礙含量。 富含甲硫胺酸之液體水流係於管柱8〇之底部被撤出。 10 如此所得液體隨後被送至分離器90，可由留在水相中 之未反應之乙内酿脈竹生產物（稱作為水性母液）中分離呈 固體形式之甲硫胺酸。 呈固體形式之甲硫胺酸係於95回收，該副產物於壓力 被調整回91後，經由進料管92而送至反應器7〇。 15 此循環回路為特佳。前述其它類型之循環為替代實施 例也全然涵蓋於本發明之範圍。 第14圖顯示根據本發明由丙烯醛製備甲硫胺酸之整個 程序。各方塊分別詳細說明於第4、5、6及13圖。 下列實例將可瞭解本發明之優點。 2〇 實例1 (試驗NCA18) 本實例顯示根據本發明製備11]^1^1^之連續方法。 所使用之材料如下： •有夾套之批次式反應器； -冷凝器管柱； 29 200811086 -msh「通氣」用滴量管； -pH電極； •導入與取樣注射器。 操作條件如下： 5 反應介質以磁力攪拌。於大氣壓進行合成。監測溫度 及PH。15.70克95%丙烯醛被導入反應器内。28.60克氫氰酸 於29.3%重量比水溶液徐緩流入反應介質中。於流入期間， 添加17.2毫升磷酸鹽緩衝液，pH 7。如此可將pH調整至4至 6 °緩衝液之添加可引發丙烯醛氰醇之合成反應。然後觀察 10 得放熱。 當全部氫氰酸皆已經被導入反應器（氫氰酸之流入結 束)後’ 35.20克甲硫醇（氣體)被添加至反應介質。此添加允 _持續合成。 當全部甲硫醇皆已經添加（如此相當於合成的結束） 15時’藉加入1N 95%硫酸讓反應介質酸化至pH=2 (反應停 止）。 於真空（4毫米汞柱）蒸發及於5(rc溫度，回收34 2〇克 HMTBN。 因此莫耳比如下： 20 MSH/丙烯醛=2.76 HCN/丙浠=1·16 分析監控允_判定反應的總產率。然後進行Hplc之分 析。反應之總產率相對於丙烯醛為95%。丙烯醛之轉化率 為100%。HMTBN之含量為98%。 30 200811086 實例2 (試驗NCA20) 本實例顯示根據本發明製備HMTBN之連續製法。 所使用之材料係與實例1相同。 反應介質以磁力攪拌。合成係於大氣壓下進行。監測 5溫度及PH。15·0克95%丙烯醛被導入反應器内。28.0克29.3% 重量比氫氰酸水溶液徐緩流入介質内。於此流入期間，添 加33克磷酸鹽緩衝液、pH 7至試驗中。如此將pH調整至pH 4至pH 6。緩衝液之添加允許引發反應來合成丙烯醛氰醇。 當全部氫氰酸皆已經導入反應器（於氫氰酸流入結束 10時），添加21.4克甲硫醇（氣體)至反應介質。 當全部甲硫醇皆已經添加時，藉加入95% 1N硫酸將反 應介質酸化至pH 2(反應停止）。 於減壓(4毫米汞柱)及5〇。(：溫度蒸發去除後，回收32.6 克 HMTBN。 15 分析監測可測定反應之總產率。然後進行HPLC分析。 反應之總產率相對於丙烯醛為96%。 實例3 本實例顯示HMTBN之工業製法，其中使用兩根吸收管 柱。 20 以丙烯醛為主之粗產物係於氣相（300-400°C )氧化丙烯 成為丙沐終之反應裔之輸出製造。此粗產物包含有溫 度之氣體混合物，該氣體混合物包含高重量百分比之難以 冷减的氣體（丙炫、氮氣、氧氣、丙稀、一氧化碳、二氧化 碳）、水、丙烯醛、丙烯酸及其它化合物。 31 200811086 然後此種以丙烯醛為主之粗產物接受處理來去除酸。 呈氣體形式之粗產物被導入洗滌管柱中，水流係循環於洗 滌管柱中。水挾帶酸。含酸液體於管柱底部被撤出。純化 後之氣體於管柱頂部被撤出。 5 如此所得氣相丙烯醛被導入吸收管柱頂部。維持於大 氣壓之此管柱也以1〇〇千克/小時流速被進給氣相氫氰酸。 如此被導入之氫氰酸係於反應器中於高溫（大於1 〇〇〇 °c溫度）由氨、甲烷及空氣藉氨氧化獲得。然後混合物經冷 卻，導入硫酸液流循環於其中之洗滌管柱，來去除過量氨。 10 於第一吸收管柱内，丙烯醛與氫氰酸間之反應係以過 量氫氰酸進行。吸收管柱的使用允許重質產物與輕質產物 的分離，藉此於反應器頂部回收最具有揮發性之產物，於 未反應之氫氰酸之情況下，該產物隨後可經循環利用。然 後氫氰酸氣相被送至其中循環水流之洗滌管杈内。於洗務 15管柱底部撤出之水溶液中的氫氰酸隨後又被送至蒸餾管 柱。如此蒸餾之氫氰酸被送至吸收管柱頂端，如此產生於 該第一吸收管柱中於水相中之氫氰酸下降液流。 須注意於氫氰酸洗滌管柱頂端丙烯之循環利用為可 能。隨後須由-氧化碳、二氧化碳、氮氣及氣氣中分離丙 20 稀。 水相中之丙烯醛液流於吸收管柱冷凝，如此於水相中 之氫氰酸下降液流起反應。 ' 因就蒸氣壓而言’如此所得水相中之丙歸駿氮醇為較 重，故於吸收官柱底部撤出’隨後再度被導入第二吸收管 32 200811086 柱頂部。 氣相中之以甲硫醇為主之粗產物也被導入第二吸收管 柱内。甲硫醇係源自於甲醇CH3OH與硫化氫H2s間之反應。 HMTBN之穩定水溶液（30%至80%重量比HMTBN)於 5 第二吸收管柱底部撤出。 實例4 進行兩次試驗(AME152及AME153)。 此等試驗顯示根據本發明之連續製造甲硫胺酸之方 法。 10 ΑΜΕ 152 程序： 下列載荷入完全經攪拌之反應器内： -59.25克檸檬酸溶液(40%)， -14.85克丙烯醛， 15 然後加入40·10克氰化鈉溶液。 放熱後5分鐘，載入15·30克曱硫醇。然後於5分鐘後， 加入275.2克水性氨液(得自ΝΗ3及NH4HC03)。 反應器加熱至150°C。 始於導入氰化鈉之總反應時間為2小時。 20 NB :檸檬酸溶液及氰化鈉溶液係用來提供氫氰酸供合 成丙烯醛氰醇。 於工業上’氫氰酸可單獨導入而非以任何鹽導入。 丙稀酸轉化度為100%。甲硫胺酸產率約為44%，甲硫 胺酸產生性產物+曱硫胺酸之產率為74%。 33 200811086 ΑΜΕ 153 程序： 下列載荷入完全經攪拌之反應器内： -58.55克檸檬酸溶液(40%)， 5 -13.95克丙稀酸， 然後加入40.55克氰化鈉溶液。Was imported. 15 Hydrocyanic acid is in the form of an aqueous solution of about 20% to 80% by weight. This solution can be prepared on the outside of the device, but it is also possible to provide water on the line. After the tubular reactor 1, there is a column 15 which circulates the hydrogen cyanide gas phase. Such a column can also adjust the amount of hydrocyanic acid introduced into the tubular reactor 1. Acryl cyanohydrin 61 is recovered at reactor output 1 and subsequently sent to tubular 20 reactor 60. Tubular reactor 60 is also fed with methyl mercaptan at 63. Also available at 64 is expected to be used to adjust the pH of the feed. After the tubular reactor 60, there is a column 65 which circulates the methyl mercaptan gas phase. Such a column can also adjust the amount of thiol that is introduced into the tubular reactor 60. 18 200811086 HMTBN aqueous solution is recovered at 62. Referring now to Figure 3 and Figures 4, 5 and 6, the method of preparation is described. This method is carried out as a first reaction step, which in the case of Figure 3 is the first reactive absorption 1. The first reactive absorption 1 is fed to a gaseous stream 2 comprising a propylene aldehyde. A gaseous stream 3 comprising hydrocyanic acid is also fed. The reaction medium flow is circulated in the absorption column 1. The pH is particularly conditioned by the feed 4 to the reaction medium stream. As detailed in Figure 4, the gaseous stream 2 comprising acrolein is derived from oxidation 20 followed by washing 25. 10 The oxidation reactor 20 is fed with propylene 21, air 22 and water 23. It is a gas phase propylene oxidation reactor. The crude product 24 is produced at the reactor output. This crude product 24 comprises a gaseous mixture comprising a high weight percentage gas (propane, nitrogen, oxygen, propylene, carbon monoxide, carbon dioxide), water, acrolein, acrylic acid and other compounds which are difficult to condense. Thus, in accordance with one embodiment of the present invention, the acid contained in the product obtained after oxidation is removed by washing 25 after the oxidation of 20 propylene 21 using air 22 in the presence of water 23 and prior to reactive absorption 1. This crude product 24 is therefore washed 25, allowing it to be removed. The crude product in the form of gas 20 24 is directed to the wash column 25, and the water stream 26 and the water stream 27 are circulated in the wash column 25. Water 26 挟 with acid. The acid-containing liquid 27 is extracted at the bottom of the washing column 25. The purified gas 2 is sent at the top of the column 25 and is directed to the reactive absorption 1. As detailed in Figure 5, the reactive absorption 1 is also fed to the hydrous cyanide 19 200811086 acid gas stream 3 ° This gaseous stream 3 is derived from the synthesis reactor 3, followed by washing. The synthesis reactor 30 is fed with ammonia 31, methane 32 and air illusion. Ammonia oxidation of methane using ammonia, for example, in the presence of air and a solid catalyst. The reaction is extremely fast. At very high temperatures. A crude product 34 rich in hydrocyanic acid is produced at reactor output 30. After cooling, this crude product 34 is obtained at reactor output 30 and then washed 35 prior to reactive absorption 1. The unreacted ammonia is removed by the aqueous sulfuric acid solution introduced into the top portion 36 of the column, and the aqueous sulfuric acid solution is circulated in the counter-flow direction in the 10 wash column 35. Ammonium sulfate is extracted at the bottom 37 of the column 35. As described in detail in Fig. 6, in the absorption device, the first step of the HMTBN synthesis according to the present invention is carried out, and the gas bear product obtained at the top of the absorption device can be partially circulated in the washing column 50, and the reaction medium 51 is flowed. It is circulated in 15 wash column 50. Device 52 allows the separation of propylene from other lighter compounds (c〇, C〇2, nitrogen, helium 2, and HCN). For example, the device can be a device that absorbs water or a compression and cooling device. Hydrogen cyanide is removed by washing (absorption) with water; propylene is recovered by condensation and distillation, or propylene is recovered from organic solvent by absorption, so it can be combined with products that cannot be condensed (carbon dioxide, carbon dioxide, nitrogen, etc.) Separation. The propylene is not contaminated (because excess propylene is not in contact with the sulphur-containing product) and can therefore be recycled, as opposed to prior art processes involving the contact of acrolein with methyl mercaptan. As explained above, this is a technical advantage of the present invention. 20 200811086 The propylene thus circulated is then directed to a feed line 21 which is fed to an oxidation reactor 20 through which acrolein is produced. Thus, in accordance with one embodiment of the present invention, the propylene cycle 53 is carried out after reactive absorption 1 to before oxidation 20. 5 The bottom of the washing column 50 is guided to the distillation column 55 by means of a tube 54. The hydrogen sulphate used in % is extracted from the top of the treatment column 55 and is guided to the absorption column 1 via the line %. According to Fig. 3, the bottom fraction of the absorption column contains acrolein which is guided to the second absorption column 6 by means of a feed tube 61. 10 A pH measuring device 65 can be provided before being introduced into the second column. This means 65 allows adjustment of the pH in the absorption column 1. If desired, a storage tank 66 for the bottoms of the column 1 can be placed before the introduction of the column 6 ,, i.e., before the start of the second step. The absorption column 6 in which the second step of the process is carried out is fed to a gaseous stream 63 containing methyl mercaptan in the form of a purified liquid or gas. The reaction medium circulates through the absorption column 60 in a manner similar to the absorption column 1. The pfj can be adjusted in particular by the feed 64 fed to the reactive medium stream of the absorption column. The HMTBN aqueous solution 62 is extracted at the bottom of the absorption column 60. This 2 〇 solution storage unit can be set. Fig. 7 shows a device for producing methionine from an industrial aqueous solution ιοί containing HMTBN. This method is carried out as a continuous aqueous phase hydrolysis 70. According to the foregoing definition, this hydrolysis does not separate or separate the intermediate product. 21 200811086 The reactor 70 is fed with an aqueous solution 101 by means of a feed pipe. Prior to introduction into the reactor 70, the aqueous phase 77 of aqueous ammonia and carbon dioxide is introduced into the aqueous solution 101 containing HMTBN via a feed tube. The pressure of the aqueous solution 1〇1 has been previously adjusted to restore the original pressure through the pump 72. The 5 HMTBN aqueous solution has a concentration of preferably greater than 30%. For example, an HMTBN solution having a concentration greater than or equal to 60% can be used. The solution also contains water and associated derivative products, primarily derived from the synthesis of HMTBN, for example from chlorocyanic acid and sulfuric acid. According to the present invention, the present synthesis is carried out using an aqueous solution of HMTBN, whereby 10 provides a number of industrial advantages. In particular, the use of an aqueous solution of HMTBN avoids the use of a stripping column (or steam distillation column) to recover the solvent. In addition, there are advantages in terms of cost and processing. According to the invention 'when the temperature is fixed', pressure is applied to have a liquid phase. The temperature in the reactor 70 is raised to 250 ° C in a stepwise manner at the mixture temperature (i.e., between 2 〇〇 c 15 and 90 ° C). According to a preferred embodiment of the invention, the synthesis is carried out at a temperature of from 20 C to 220 C. For aqueous phase operation, the pressure must be from 5 to 100 bar (preferably about 20 bar). During the reaction, the temperature within the reaction was raised from the temperature of the mixture (i.e., to between 90 ° C) to the plateau temperature. 20 At the input end of Reaction Benefit 70, the HMTBN/NH3 molar ratio is between 1/5 and 1/50, for example about 1/20, followed by a molar excess of aqueous ammonia relative to hwtbn. The molar ratio of HMTBN/C〇2 is! To 1/2 inch, for example, the input of reactor 70 is about 1/10 or 1/3. It mainly contains methionine, carbon dioxide and ammonia in a dissolved form of water-soluble 22 200811086 liquid recovered at 73. Fig. 8 shows a device for producing methionine from an industrial aqueous solution 1HM1 containing HMTBN. The reactor 70 is fed to the aqueous solution 101 by means of a feed tube. 5 Prior to introduction into the reactor, the aqueous phase 77 of aqueous ammonia and carbon dioxide is introduced into the aqueous solution 101 containing HMTBN via a feed tube. The pressure of the aqueous solution 1 〇 has been previously adjusted to restore the original pressure through the pump 72. The HMTBN aqueous solution has a concentration of preferably greater than 30%. For example, an HMTBN solution having a concentration greater than or equal to 60% can be used. The solution also contains water and related derivative products, mainly derived from the synthesis of HMTBN, for example from hydrogen cyanide and sulfuric acid. According to the present invention, the present synthesis is carried out using an aqueous solution of HMTBN, thereby providing a number of industrial advantages. In particular, the use of an aqueous solution of HMTBN avoids the use of a stripping column (or steam distillation column) to recover the solvent. In addition, there are advantages in terms of cost and location. According to the invention, when the temperature is fixed, a pressure is applied to have a liquid phase. The temperature at which the reaction is 70 is ramped up to 250 ° C in the stepwise manner at the mixture temperature (i.e., between 2 Torr and 90 to 90 ° C). According to a preferred embodiment of the invention, the synthesis is carried out at a temperature of from 20 C to 220 °C. For aqueous phase operation, the pressure must be from 20 5 to 100 bar (preferably about 2 bar). During the reaction, the temperature in the reactor is raised from the temperature of the mixture (i.e., between 2 〇〇c and 90 C) to the plateau temperature. At the input of Reaction Benefit 70, the hrtbn/NH3 molar ratio is still between 1/5 Torr, for example about 1/20; and then with aqueous ammonia being relatively large relative to HMTBN2. The molar ratio of HMTBN/C〇2 is from 1 to 1/20, for example about 1/10 or 1/3 at the input of reactor 70. The output 73 comprising mainly methionine, carbon dioxide and ammonia in dissolved form is obtained by hydrolysis of HMTBN at the outlet of reactor 70. This mixture is reduced in pressure, e.g., to atmospheric pressure, prior to being introduced into the stripping column 80 (also referred to as a steam-steam column), for example, using a pressure reducing valve 74. In column 80, the introduced reduced pressure mixture is separated into a methionine-rich liquid stream 82 and a gaseous stream 81 rich in ammonia and carbon dioxide. 10 At the top of column 80, ammonia and carbon dioxide are also included and water and gaseous streams are condensed into stream 83. Stream 83 is then stored at 84. The storage tank 84 includes an exhaust port 85 as needed. According to the present invention, the term "ammonia" is intended to mean a phase substantially containing NH3; the term "aqueous ammonia" is intended to mean a phase substantially containing NH4OH. 15 m in the same way, 'when referring to the "gas phase containing carbon dioxide", the intention is to express a phase containing carbon monoxide in the form of gas sorrow; and when referring to the "aqueous phase containing carbon dioxide", it is intended to mean the phase containing h2co3 in essence. . The term "substantially" indicates that the phase of interest contains an excess of the compound under consideration, which is greater than 50%, more particularly greater than 70%. 20 The aqueous phase containing the aqueous gas and the niobium oxide 7 is recycled to the hydrolysis reactor 7 by means of a feed line 77 after its pressure has been adjusted again. According to the invention, a feed pipe 75 can also be provided before the pressure is again adjusted back, which feeds the ammonia, carbon dioxide and/or water to the feed pipe 77. Such a feed tube allows adjustment of ammonia, carbon dioxide and/or water 24 200811086 if required. The liquid stream containing methionine, i.e., the citrate, i.e., the aqueous solution of the reduced methionine, is withdrawn from the bottom of the stripping column 80 by means of a withdrawal tube 82. 5 This liquid is cooled in heat exchanger 86 to precipitate methionine. However, any means known to those skilled in the art, including evaporation, can also be applied at any point. The liquid thus obtained is sent to the separator 90, thereby allowing the unreacted product which is less produced by the HMTBN to remain in the aqueous phase (referred to as the aqueous mother liquor) to separate the methionine in a solid form. The methionine in solid form is recovered at 95, and the aqueous mother liquor 92 is sent to the reactor 70 via the feed line 92 after the pressure has been adjusted by the pump 91. This type of circulation loop is particularly good. Figure 9 shows another cycle possibility in accordance with the present invention. 15 At 92, the thiline-producing product can be chemically treated or enzymatically catalyzed prior to recycling. The methionine-producing product can be recycled to the hydrolysis reactor 70' to the stripping column 8 or recycled to the withdrawal tube. According to one embodiment of the invention, the aqueous mother liquor 92 is recycled after chemical treatment or enzymatic treatment. The cycle can be carried out, for example, to the column 8 or to the stream 82. According to the present invention, the aqueous mother (4) is naturally recycled to the reactor 70 without chemical treatment or enzymatic treatment. As shown in FIG. 1 , according to one embodiment of the present invention, the synthesis of methionine is carried out in a tubular reactor or a plurality of stirred reverse 25 200811086 reactors 710, 720, 730 and 740. In progress. The number of stirred reactors is not particularly limited. The preferred system is greater than 3, but there is no limit to the number of Yuan Da. According to one embodiment of the invention, the methionine-rich stream 82 is separated by fractional crystallization 91, thus first obtaining solid methionine 95 and second obtaining aqueous mother liquor 92. Segmented crystals 91 also produce a gaseous stream 92 which is referred to as a "concentrated product" of aqueous and light products. After condensation 93, stream 94 can be stored as needed. Figure 11 shows a device for preparing methionine from a propylene disk. The preparation of the HMTBN solution contained two tubular reactors 1 and 6. The first step of the method, that is, the synthesis of acrolein by acrolein and hydrocyanic acid is carried out in a tubular reactor i; and the second step of the process of the invention, that is, the addition of MSH to the acrolein obtained in the first step The cyanohydrin is carried out in the reactor 6. While Figure 11 shows two reactors in tubular form, it is contemplated in accordance with the present invention that such steps are carried out in a stirred reactor or batch reactor or any other suitable reactor. The tubular reactor 1 is fed with acrylic acid at 2, and the hydrocyanic acid is fed at 3. The molar ratio of hydrocyanic acid/acrolein is from 1 to 1 Torr and preferably from 1 to 3. Feeds intended to adjust pH can also be provided at 4 and constitute the primary feature of the present invention. According to one embodiment of the invention, a pH adjusting solution, such as a buffer solution, is introduced after mixing with other streams, 2 and 3. The hydrocyanic acid is introduced as an aqueous solution in the form of, for example, about 5% to 90% by weight of an aqueous solution. This solution can be prepared on the outside of the unit, but can also be supplied on the water line 26 200811086 5 . The cyanohydrin 61 is recovered at the output of the reactor 1 and then sent to the tubular reactor 60. Tubular reactor 60 is also fed to MSH at 63. Also provided at 64 is a feed intended to adjust the pH. The HMTBN aqueous solution was recovered at 62. • The method also implements a third step 70. An aqueous phase containing aqueous ammonia and carbon dioxide is added to the aqueous solution 62 containing HMTBN through the feed pipe 77 before being introduced into the reactor. 10 An aqueous solution containing HMTBN, aqueous ammonia and carbon dioxide was introduced into the reactor 70 after the pressure of 72 was adjusted back. A mixture 73 comprising methionine, carbon dioxide and ammonia in dissolved form is recovered from the output of reactor 70. 15 • A method for preparing methionine from acrolein will now be described with reference to Figs. 12 and 13. The difference between the two figures and the eleventh figure is the implementation method shown. In a device similar to that of Figure 11, the preparation of the HMTBN solution according to Figure 12 or Figure 13 involves two reactors 1 and 6〇. The first step of the process is carried out in a tubular reactor 1, and the second step of the process of the invention is carried out in a reactor 60. 20 After the reactor 1, there is a column 15, in which cyanohydrin is fed, and the circulation of the hydrogen cyanide gas phase is allowed. This column can also adjust the amount of hydrocyanic acid introduced into the reactor 1. Acryl cyanohydrin 61 is recovered at the output of column 15 and sent to tubular reactor 60. 27 200811086 By the same token, the HMTBN is sent to the column 65 at the output of the reactor 60. This allows recycling of unreacted products. The difference between the device of Figure 13 and the device of Figure 12 is that the third step is stated. An aqueous phase 77 containing aqueous ammonia and carbon dioxide is added to the aqueous solution 62 containing hydrazine. The pressure of the entire mixture is adjusted back to the original pressure by the pump 72. The reactor 70 is also fed to an aqueous solution 71, that is, an industrial solution mainly comprising carbendazim thiourea, but also a derivative product related to the production of methionine, that is, ureidoacetic acid, Ubium succinimide and 2-amino-based (methylthio)butanamine (also known as hydrazine). The term "methionine production" is intended to mean any compound which can be produced by the hydrolysis of ammonia to produce methionine. According to the present invention, the aqueous solution of carbendazim which is itself a methionine-producing compound also contains a methionine-producing derivative 15 product, particularly the above-mentioned ureidoacetic acid, urea succinimide and 2-amino group. · 4_(Methylthio)butanamine. By definition, methionine is not included in the methionine-producing compound. The output of the reactor 70 is obtained as an output product comprising mainly methionine, carbon dioxide and ammonia in dissolved form. 20 In the column 8 ,, the introduced reduced pressure mixture is separated into a methionine-rich liquid stream 82 and a gaseous stream 81 rich in ammonia and carbon dioxide. At the top of the column 80, a gaseous stream 81 rich in ammonia and carbon dioxide, also containing water, is condensed and then stored at 84. The reservoir 84 can include an vent 85 as desired. 28 200811086 Part of the ammonia gas is condensed. The aqueous phase of aqueous ammonia and carbon dioxide is recycled to the reactor after the pressure is adjusted back to 76. Thus, in accordance with an embodiment of the present invention, after condensation, the stream 81 rich in gas and carbon dioxide is stored 84 and is recycled to the third step after the pressure is adjusted back to 76. According to the invention, a feed tube 75 can also be provided which feeds ammonia and/or carbon dioxide before the pressure is adjusted back. Such a feed tube also allows adjustment of the ammonia content and/or the oxidizing content if desired. The liquid stream of methionine-rich liquid is withdrawn at the bottom of the column 8〇. The liquid thus obtained is then sent to a separator 90, and the methionine in solid form can be separated from the unreacted B. sinensis product (referred to as an aqueous mother liquor) remaining in the aqueous phase. The methionine in solid form is recovered at 95. The by-product is adjusted back to 91 after pressure and sent to reactor 7 via feed line 92. 15 This loop is especially good. The foregoing other types of cycles are also within the scope of the invention as alternative embodiments. Figure 14 shows the entire procedure for the preparation of methionine from acrolein in accordance with the present invention. The blocks are detailed in Figures 4, 5, 6 and 13 respectively. The advantages of the invention will be appreciated from the following examples. 2 〇 Example 1 (Test NCA 18) This example shows a continuous process for the preparation of 11]^1^1^ in accordance with the present invention. The materials used are as follows: • a jacketed reactor with a jacket; - a condenser column; 29 200811086 -msh "aeration" with a drop tube; - pH electrode; • an introduction and sampling syringe. The operating conditions are as follows: 5 The reaction medium is magnetically stirred. The synthesis is carried out at atmospheric pressure. Monitor temperature and pH. 15.70 grams of 95% acrolein was introduced into the reactor. 28.60 g of hydrocyanic acid was slowly introduced into the reaction medium at a 29.3% by weight aqueous solution. During the influx, 17.2 ml of phosphate buffer, pH 7, was added. Thus, the addition of a pH adjusted to 4 to 6 ° buffer can initiate the synthesis of acrolein. Then observe 10 to get an exotherm. When all of the hydrocyanic acid had been introduced into the reactor (end of hydrogen cyanide ingress), 35.20 grams of methyl mercaptan (gas) was added to the reaction medium. This addition allows _ continuous synthesis. When all of the methyl mercaptan has been added (so equivalent to the end of the synthesis) at 15 o', the reaction medium is acidified to pH = 2 by adding 1 N of 95% sulfuric acid (reaction stop). Evaporate in a vacuum (4 mm Hg) and recover 34 2 g of HMTBN at 5 rc. Therefore, the molars are as follows: 20 MSH / acrolein = 2.76 HCN / propionate = 1 · 16 Analytical monitoring allowed judgment The total yield was then analyzed by Hplc. The total yield of the reaction was 95% relative to acrolein. The conversion of acrolein was 100%. The content of HMTBN was 98%. 30 200811086 Example 2 (Test NCA20) This example A continuous process for the preparation of HMTBN according to the present invention is shown. The materials used are the same as in Example 1. The reaction medium is magnetically stirred. The synthesis is carried out under atmospheric pressure. The temperature and pH are monitored. 15·0 g of 95% acrolein is introduced into the reaction. 28.0 g 29.3% by weight of aqueous solution of hydrocyanic acid slowly flowed into the medium. During this inflow, 33 g of phosphate buffer was added, pH 7 to the test. The pH was adjusted to pH 4 to pH 6. The buffer was adjusted. The addition allows the reaction to be initiated to synthesize acrolein. When all of the hydrocyanic acid has been introduced into the reactor (at the end of the hydrocyanic acid inflow of 10), 21.4 grams of methyl mercaptan (gas) is added to the reaction medium. When the alcohol has been added, add 95% 1N sulfuric acid acidified the reaction medium to pH 2 (stopping of the reaction). Under reduced pressure (4 mm Hg) and 5 Torr. (: After evaporation by evaporation, 32.6 g of HMTBN was recovered. 15 Analytical monitoring The total yield of the reaction was determined. Then, HPLC analysis was carried out. The total yield of the reaction was 96% relative to acrolein. Example 3 This example shows an industrial process for HMTBN in which two absorption columns are used. 20 Acrylaldehyde-based crude product is in the gas phase ( 300-400 ° C) propylene oxide is produced as the output of the reaction of the end of the propylene. The crude product contains a gas mixture of temperature, which contains a high percentage by weight of gas that is difficult to cool (cyan, nitrogen, oxygen, Propylene, carbon monoxide, carbon dioxide, water, acrolein, acrylic acid and other compounds. 31 200811086 This crude product, mainly acrolein, is then treated to remove the acid. The crude product in gaseous form is introduced into the wash column. The water flow is circulated in the washing column. The water is acid. The acid-containing liquid is withdrawn at the bottom of the column. The purified gas is withdrawn at the top of the column. It is introduced into the top of the absorption column. The column maintained at atmospheric pressure is also fed to the gas phase hydrocyanic acid at a flow rate of 1 〇〇 kg / hr. The hydrocyanic acid thus introduced is in the reactor at a high temperature (greater than 1 〇). 〇〇°c temperature) is obtained by ammonia oxidation of ammonia, methane and air. The mixture is then cooled and introduced into the washing column in which the sulfuric acid stream is circulated to remove excess ammonia. 10 In the first absorption column, acrolein The reaction with hydrocyanic acid is carried out with excess hydrocyanic acid. The use of an absorption column allows the separation of the heavy product from the light product, thereby recovering the most volatile product at the top of the reactor, in the unreacted hydrogen. In the case of cyanic acid, the product can then be recycled. The hydrogen cyanide gas phase is then sent to the wash tube where the circulating water stream is passed. The hydrocyanic acid in the aqueous solution withdrawn from the bottom of the column 15 is then sent to the distillation column. The hydrogen cyanide thus distilled is sent to the top of the absorption column, thus producing a hydrocyanic acid falling liquid stream in the aqueous phase in the first absorption column. Attention should be paid to the recycling of propylene at the top of the hydrocyanic acid scrubbing column. The propylene oxide must then be separated from carbon monoxide, carbon dioxide, nitrogen and gas. The acrolein solution in the aqueous phase is condensed on the absorption column, and the hydrocyanate descending liquid in the aqueous phase is reacted. 'Because of the vapor pressure', the acryl alcohol in the aqueous phase thus obtained is heavier, so it is withdrawn at the bottom of the absorption column and then re-introduced into the top of the second absorption tube 32 200811086 column. The crude product mainly composed of methyl mercaptan in the gas phase is also introduced into the second absorption column. The methyl mercaptan is derived from the reaction between methanol CH3OH and hydrogen sulfide H2s. A stable aqueous solution of HMTBN (30% to 80% by weight HMTBN) is withdrawn at the bottom of the 5 second absorption column. Example 4 Two tests (AME 152 and AME 153) were performed. These tests show the method of continuously producing methionine according to the present invention. 10 152 152 Procedure: Load the following into a fully stirred reactor: -59.25 g citric acid solution (40%), -14.85 g acrolein, 15 then add 40.10 g sodium cyanide solution. Five minutes after the exotherm, 15·30 g of hydrazine thiol was loaded. Then, after 5 minutes, 275.2 g of aqueous ammonia (from ΝΗ3 and NH4HC03) was added. The reactor was heated to 150 °C. The total reaction time starting from the introduction of sodium cyanide was 2 hours. 20 NB: A citric acid solution and a sodium cyanide solution are used to provide hydrocyanic acid for acrolein. Industrially, hydrocyanic acid can be introduced separately rather than with any salt. The degree of conversion of acrylic acid is 100%. The yield of methionine was about 44%, and the yield of methionine producing product + guanidine thioglycol was 74%. 33 200811086 ΑΜΕ 153 Procedure: Load the following into a fully stirred reactor: -58.55 grams of citric acid solution (40%), 5 - 13.95 grams of acrylic acid, then add 40.55 grams of sodium cyanide solution.
放熱後5分鐘，載入13.40克甲硫醇。然後於5分鐘後， 加入210.9克水性氨液(得自ΝΗ3及NH4HC〇3)。 反應器加熱至150°C。 10 始於導入氰化鈉之總反應時間為2小時。 NB :擰檬酸溶液及氰化鈉溶液係用來提供氫氰酸供合 成丙烯酸氰醇。 於工業上’氫氰酸可單獨導入而非以任何鹽導入。 丙烯醛轉化度為100%。甲硫胺酸產率約為45〇/〇,曱硫 15胺酸產生性產物+曱硫胺酸之產率為75%。 【圖式簡單說明】 第1、2及3圖以非限制性方式表示根據本發明由丙烯醛 製備HMTBN之溶液之三個裝置。 20 第4至6圖顯示第3圖製備HMTBN之裝置之某歧部八 第7及8圖示意顯示根據本發明由HMTBN製備甲辟胺 酸之兩種裝置 第9及1〇圖示意顯示根據本發明由hmTBN製備ψ ☆ 酸之裝置之其它實施例。 ’丨〔胺 第11至14圖示意顯示根據本發明由丙烯醛製僑甲碲 34 200811086 酸之四種裝置。 【主要元件符號說明】Five minutes after the exotherm, 13.40 g of methyl mercaptan was loaded. Then, after 5 minutes, 210.9 g of aqueous ammonia (from ΝΗ3 and NH4HC〇3) was added. The reactor was heated to 150 °C. 10 The total reaction time from the introduction of sodium cyanide was 2 hours. NB: The citric acid solution and the sodium cyanide solution are used to provide hydrocyanic acid to form cyanohydrin. Industrially, hydrocyanic acid can be introduced separately rather than with any salt. The degree of acrolein conversion was 100%. The yield of methionine was about 45 Å/〇, and the yield of hydrazine thiol acid producing product + hydrazine thioglycol was 75%. BRIEF DESCRIPTION OF THE DRAWINGS Figures 1, 2 and 3 show, in a non-limiting manner, three means for preparing a solution of HMTBN from acrolein according to the present invention. 20 Figures 4 to 6 show a certain portion of the apparatus for preparing HMTBN in Fig. 3. Figures 7 and 8 are schematic diagrams showing the ninth and first schematic diagrams of two devices for preparing methamamine by HMTBN according to the present invention. Other embodiments of the apparatus for preparing ψ ☆ acid from hmTBN in accordance with the present invention.丨 [amines Figures 11 to 14 schematically show four devices for the preparation of acid from acrolein according to the invention 34 200811086. [Main component symbol description]
1.. .管狀反應器 1.. .吸收裝置、吸收管柱 1.. .第一反應性吸收管柱 2.. .丙烯醛進料流 3.. .氫氰酸進料流 4.. . pH調節用進料 15…管柱 20…氧化 20·.·氧化反應器 21.. .丙烯 21.. .進料管 22.. .空氣 23…水 24.. .粗產物 25.. .洗滌 26…水 27.. .含酸之液體 30.. .合成反應器 31···氨 32.. .甲烷 33.. .空氣 34.. .粗產物 35.. .洗滌 36.. .管柱頂部 37.. .管柱底部 50.. .洗滌管柱 51…反應介質流 52.. .分離裝置 53.. .管路 54.. .管路 55.. .蒸餾管柱 56.. .管路 60.. .管狀反應器 60…第二吸收管柱 61.. .進給管1.. tubular reactor 1.. absorption device, absorption column 1.. first reactive absorption column 2. acrolein feed stream 3.. hydrocyanate feed stream 4.. pH adjustment feed 15... column 20...oxidation 20·.·oxidation reactor 21.. propylene 21.. feed tube 22.. air 23...water 24...crude product 25.. Washing 26...water 27.. Acid-containing liquid 30.. Synthesis reactor 31···Ammonia 32.. Methane 33.. Air 34... Crude product 35.. Washing 36.. Tube Column top 37.. Column bottom 50.. Wash column 51... Reaction medium flow 52.. Separation device 53.. Line 54.. Line 55.. Distillation column 56.. Pipeline 60.. tubular reactor 60... second absorption pipe column 61.. feed pipe
61.. .丙浠醛氰醇 62·.·回收HMTBN 62.. .HMTBN 水溶液 62…含ΗΜ1ΈΝ之水溶液 63…進給甲硫醇 63.. .甲硫醇進料流 64.. . pH調節用進料 65.. .管柱 70.. .反應器 35 200811086 70...水解反應器 83...液流 70…第三步驟反應器 84...儲存槽 71...水溶液 85...排氣口 72...幫浦 86...熱交換器 73...回收混合物 90...分離器 73...回收、輸出混合物 91…幫浦 74...減壓閥 92...進料管、水性母液 75...進料管 93…冷凝 76…幫浦 94...液流 77…水相 95.··回收曱硫胺酸 77...進料管 101…包含HMTBN之工業用水 80...管柱 溶液 81…富含氨和二氧化碳之氣態流 710-740…經攪拌之反應器 82...富含甲硫胺酸之液流 901-904...分段結晶 3661.. . Acrylonitrile cyanohydrin 62 ··Recovering HMTBN 62.. .HMTBN Aqueous solution 62...aqueous solution containing ΗΜ1ΈΝ63...feeding methyl mercaptan 63..methyl mercaptan feed stream 64.. pH adjustment Feed 65.. column 70.. .reactor 35 200811086 70...hydrolysis reactor 83...liquid stream 70...third step reactor 84...storage tank 71...water solution 85. .. Exhaust port 72 ... pump 86 ... heat exchanger 73 ... recovery mixture 90 ... separator 73 ... recovery, output mixture 91 ... pump 74 ... pressure reducing valve 92 ...feeding tube, aqueous mother liquor 75...feeding tube 93...condensing 76...helping pump 94...liquid stream 77...aqueous phase 95.··recovering 曱 thiamic acid 77...feeding tube 101 ...industrial water containing HMTBN 80...column solution 81...gaseous stream of ammonia and carbon dioxide 710-740... stirred reactor 82... methionine-rich liquid stream 901-904.. Sectional crystallization 36
Claims (1)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0606295 | 2006-07-11 | ||
| FR0606294A FR2903690B1 (en) | 2006-07-11 | 2006-07-11 | PROCESS FOR THE PREPARATION OF METHIONINE FROM ACROLEIN WITHOUT ISOLATING INTERMEDIATE PRODUCTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW200811086A true TW200811086A (en) | 2008-03-01 |
Family
ID=38687477
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW96125214A TW200811086A (en) | 2006-07-11 | 2007-07-11 | Process for preparing 2-hydroxy-4-(methylthio)butyronitrile and methionine |
Country Status (2)
| Country | Link |
|---|---|
| TW (1) | TW200811086A (en) |
| WO (1) | WO2008006977A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101977844B (en) * | 2008-03-20 | 2014-04-02 | 阿肯马法国公司 | Process for producing hydrocyanic acid |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2939791B1 (en) | 2008-12-16 | 2011-01-14 | Adisseo France Sas | PROCESS FOR THE PREPARATION OF ACROLEIN FROM GLYCEROL OR CRUDE GLYCERIN |
| FR2954312B1 (en) * | 2009-12-21 | 2012-02-10 | Adisseo France Sas | PROCESS FOR THE PREPARATION OF ACROLEIN BY CATALYTIC DEHYDRATION OF GLYCEROL OR GLYCERIN |
| FR2961507B1 (en) | 2010-06-17 | 2016-03-04 | Adisseo France Sas | PROCESS FOR THE PREPARATION OF ACROLEIN FROM GLYCEROL OR GLYCERIN |
| EP2848607A1 (en) | 2013-09-17 | 2015-03-18 | Evonik Industries AG | Method for extracting methionine |
| FR3041659B1 (en) | 2015-09-30 | 2017-10-20 | Arkema France | PROCESS FOR PRODUCING L-METHIONINE |
| FR3041658B1 (en) | 2015-09-30 | 2017-10-20 | Arkema France | PROCESS FOR PRODUCING L-METHIONINE |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1934838A (en) * | 1930-04-14 | 1933-11-14 | Ig Farbenindustrie Ag | Production of hydrocyanic acid |
| GB605311A (en) * | 1945-04-17 | 1948-07-20 | Us Ind Chemicals Inc | Improvements in the manufacture of methionine |
| US2879188A (en) * | 1956-03-05 | 1959-03-24 | Westinghouse Electric Corp | Processes for making transistors |
| DE1014094B (en) * | 1956-05-18 | 1957-08-22 | Basf Ag | Process for the preparation of cyanohydrins |
| US4069251A (en) * | 1969-02-08 | 1978-01-17 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Continuous process for the manufacture of methionine |
| CH529118A (en) * | 1969-02-08 | 1972-10-15 | Degussa | Process for the production of methionine |
| US5925794A (en) * | 1993-06-08 | 1999-07-20 | Novus International, Inc. | Process for the preparation of 3-(methylthio)propanal |
| FR2733231B1 (en) * | 1995-04-24 | 1997-07-04 | Rhone Poulenc Nutrition Animal | PROCESS FOR CONDENSING CYANHYDRIC ACID WITH AN ALDEHYDE |
| DE19547236A1 (en) * | 1995-12-18 | 1997-07-03 | Degussa | Process for the preparation of D, L-methionine or its salt |
| DE10238212A1 (en) * | 2002-08-21 | 2004-03-04 | Degussa Ag | Process for the preparation of α-amino acids by hydrolysis of hydantoins at elevated pressure and temperature |
-
2007
- 2007-07-11 TW TW96125214A patent/TW200811086A/en unknown
- 2007-07-11 WO PCT/FR2007/001189 patent/WO2008006977A1/en active Application Filing
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101977844B (en) * | 2008-03-20 | 2014-04-02 | 阿肯马法国公司 | Process for producing hydrocyanic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008006977A1 (en) | 2008-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW200811086A (en) | Process for preparing 2-hydroxy-4-(methylthio)butyronitrile and methionine | |
| US10894766B2 (en) | Process for the production of alkanesulfonic acids | |
| AU765481B2 (en) | Method of producing alkane sulfonic acid | |
| US9403764B2 (en) | Method of production of a methionine salt | |
| RU2595039C2 (en) | Method of producing methyl mercaptopropyl aldehyde | |
| US20060016334A1 (en) | Process for purifying CO2 gas streams | |
| US10899706B2 (en) | Method for preparing methionine | |
| EP2521710B1 (en) | A urea stripping process for the production of urea | |
| EP2379495B1 (en) | Improving cumene oxidation | |
| US20240043375A1 (en) | Process for producing urea and biuret | |
| TW202233566A (en) | Optimized process for preparing alkyl methacrylate by reducing the level of troublesome by-products | |
| TW202233568A (en) | Optimized process for preparing methacrylic acid (ma) and/or alkyl methacrylate by reducing the level of troublesome by-products | |
| FR2903690A1 (en) | Making 2-hydroxy-4-(methylthio)butyronitrile aqueous solution from acrolein, useful to prepare methionine, comprises reacting acrolein with hydrocyanic acid and methylmercaptan | |
| CN112512973B (en) | Method for purifying hydrogen cyanide | |
| JPH03169843A (en) | Purification of crude cyanhydrin | |
| WO2007034066A1 (en) | Continuous synthesis of methionine from 2-hydroxy-4-(methylthio)butyronitrile, co2, nh3 and h2o without the isolation of intermediate products | |
| US20220048855A1 (en) | Method for producing methionine | |
| CN112320819B (en) | Effective method for detoxifying cyanide-containing waste gases and waste waters in a process for producing alkali metal cyanides | |
| JPH1025273A (en) | Production of acetone cyanhydrin | |
| JP2011201784A (en) | Manufacturing method of acrylonitrile | |
| JPS5840941B2 (en) | Method for producing alkylamines | |
| WO2007034064A1 (en) | Continuous synthesis of an $g(a)-amino acid from a cyanhydrin of $g(a)-amino acid without the isolation of intermediate products | |
| Hasselbach et al. | Process for purifying CO 2 gas streams | |
| JPS63162646A (en) | Production of monochloroacetone |