201041840 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明係有關於一種精笨-田4 产缺 一甲酸生產工藝中排放的工藝 氣體進行有效的處理及回妆 吹的方法，特別有關於一種去 除排放氣體的有害雜質，回 ^卜 從精本二曱酸工廠排放氣體 中的氫氣的方法。 【先前技術3 [0002] 此處先簡單介紹典型的純對笨_甲酸生 ' ; 本專利進行說明，典型步驟如下. π ' ； [0003] 1.通過逐級升溫和升壓的悟、、w， 兄下’使不純的粗對苯二甲 酸完全溶解在水中。 % [0004] 2·溶液最終達到一定的溫唐釦疲表各 ^ 風度和壓力，在聰族金屬和過量 的氫氣存在下’歧__笨4数存在的雜質進 打氫化還原反應’將4-縣苯甲料雜質還原成易與對 苯二曱酸分離的如甲基苯曱酸等物質^ [0005] 3.通過降低被處理過溶液的壓力，以一步或多步逐級系 列降壓使對本一甲酸晶體結晶出來，水和溶解的惰性氣 體或其他有機雜質蒸發後形成含有水蒸氣、惰性氣體、 未反應的過量的氫氣和揮發的雜質的排放氣流。 [0006] 4.為了有效地利用結晶所產生的熱能，工藝中常使用該 部分排放氣流作為不純對苯二曱酸溶解時預熱使用，使 其中大部分的水蒸氣被冷凝下來，但其中仍舊含有大量 的水蒸氣、氫氣、一氧化碳和其他揮發的氣體。 [0007] 現有的工藝大多將這些剩餘排放氣體直接排放到大氣中 098116489 表單編號Α0101 第3頁/共16頁 0982027942-0 201041840 ’沒有對其中的氫氣進行回收利用，造成了資源的浪費 。本專利所提及的精鄰苯二甲酸或精㈣二甲酸生產工 藝基本與精對苯二甲酸類似，在此不細述 [0008] [0009] 中國大陸第CN1264360A號專利中提 出了 一種處理並回收 精對苯二甲酸瑞排放氣流中氫氣的方法，將排放氣流 中—氧化碳和水蒸汽轉化成二氧化碳和氫氣，提高氮氣 的純度，但是該專利在使用轉化爐或缝吸附方式對氮 氣純化過程之前，並沒錄Μ效的措施絲排放氣流 中存在的、包括笨甲酸、對甲基笨甲酸、苯二甲酸等有 機物質，這錄質會錢彳㈣冷巾赌結晶並 因此對轉化爐及變壓吸附系統造成床廣堵塞產生嚴重的 影響；同時，排放氣流中存在的有機物將會對氧化 鋼等組劑產生嚴重的影響；因此，未經有害物 質處理就直接轉化的工藝是不可行的。另外，該專利的 說明書還指出可以使用甲私反應將―氧化碳轉化為甲 烷氣來除去一氧化碳，但在實際的操作遠程中新生成 的甲烧氣錢· __，也將造錢化反應中的Pd_ C觸媒暫時性失活’影響氫化反應器正常反應。此外回 收得到的氫氣濃度也不能保證一定符合後續工藝的要求 【發明内容】 本發明的目的在於提供一種回收精苯二甲酸工廠排放氣 流中氫氣的方法，以解決現有技術中存在的上述問題。 本發明通過域洗處理去除精苯二曱酸結晶過程中排放的 工藝氣體中的酸性物質及高沸點易結晶物質，使其可安 098116489 表單編號A0101 第4頁/共16頁 0982027942-0 201041840 [0010] [0011] [0012] [0013] Ο [0014] Ο [0015] [0016] 全地應用於後續工藝。 本發明提供的技術方案如下： 一種回收精苯二甲酸工廠排放氣流中氫氣的方法，包括 以下步驟： al.將苯二甲酸重結晶時直接得到的排放氣體保持在2〇〇 C至3 0 0 °C用少量喊溶液域洗處理。 a2.將苯二甲酸重結晶時直接得到的排放氣體保持在2〇〇 C至300 C用少量碱溶液減洗處理，碱洗處理後的氣體引 入轉化爐中；轉化爐溫度控制在200«>c至3〇(rc，壓力為〇 至4. 6Mpa，用甲醇裂解催化劑催化，將氣體中的一氧化 碳與水蒸氣反應轉化產生氫氣。 a3.將笨二甲酸重結晶時直接得到的排放氣體保持在200 °(：至3〇0°(：用少量雜液域洗處理，喊洗處理後的氣體引 入轉化爐中；轉化爐溫度控制奔200°C至30(TC，壓力為0 至4. 6Mpa向轉化爐中引入甲醇蒸氣，用甲醇裂解催化 劑催化，將氣財的—氧彳巧和曱料氣與水蒸氣反應 轉化產生氫氣。 b.將經步驟al、a2sta3處理後的排放氣體引人換熱器或 冷卻塔中，將可凝性氣體冷凝下來；再將得到的富氫氣 流引入變壓吸附裝置，除去富氫氣流中的其他雜質，得 到氫氣濃度在99.99 wt%以上’ -氧化碳濃度5 ppm wt的純的氫氣回收氣流。 其中，錄測’在笨二甲酸重結晶時直接得到的排放氣 098116489 表單編號A0101 第5頁/共16頁 0982027942-0 201041840 體中的一氧化碳占除水以外的氣體總量的含量3〇〇〇PPm wt時，進入步驟al或a3處理；經檢測，在笨二甲酸重^ 晶時直接得到的排放氣體中的一氧化碳占除水以外的氣 體總量的含量>3000ppm wt時進入步驟a2或a3處理’其 中’ al、a2和a3為任選一的步驟，排放氣體或經過步驟 al到步驟b ;或經過步驟a2到步驟b ;或經過步驟a3到步 [0017] 對排放氣體進行碱洗處理可保證後續工序正常進行，優201041840 VI. Description of the Invention: [Technical Field of the Invention] [0001] The present invention relates to a method for effectively treating and returning makeup gas discharged from a process of producing a singular-formaldehyde-deficient formic acid production process, particularly Regarding a kind of harmful impurities for removing exhaust gas, a method of discharging hydrogen from a gas from a crude dipic acid plant is returned. [Prior Art 3 [0002] Here is a brief introduction to the typical pure pair of stupid_formic acid'; this patent is described, the typical steps are as follows. π '; [0003] 1. Through the step-by-step temperature rise and boost, w, Brother's 'dissolve impure crude terephthalic acid completely dissolved in water. % [0004] 2· The solution finally reaches a certain temperature and pressure, and in the presence of Cong metal and excess hydrogen, 'discrimination __ stupid 4 number of impurities in the hydrogenation reduction reaction' will be 4 - The county benzene material impurity is reduced to a substance such as methyl benzoic acid which is easily separated from terephthalic acid. [0005] 3. By reducing the pressure of the treated solution, stepping down step by step or step by step The crystal of the present formic acid is crystallized, and water and dissolved inert gas or other organic impurities are evaporated to form an exhaust gas stream containing water vapor, an inert gas, unreacted excess hydrogen, and volatile impurities. [0006] 4. In order to effectively utilize the heat energy generated by crystallization, the part of the exhaust gas stream is often used in the process as preheating for the dissolution of impure terephthalic acid, so that most of the water vapor is condensed, but still contains A large amount of water vapor, hydrogen, carbon monoxide and other volatile gases. [0007] Most of the existing processes directly discharge these remaining exhaust gases into the atmosphere. 098116489 Form No. 1010101 Page 3 of 16 0982027942-0 201041840 ‘There is no recycling of hydrogen, resulting in waste of resources. The production process of purified phthalic acid or refined (tetra)dicarboxylic acid mentioned in this patent is basically similar to that of purified terephthalic acid, and will not be described in detail herein [0008] [0009] A treatment is proposed in the Chinese Patent No. CN1264360A. The method for recovering hydrogen from the purified terephthalic acid sulphur gas stream converts carbon monoxide and water vapor into carbon dioxide and hydrogen in the exhaust gas stream to increase the purity of the nitrogen gas, but the patent uses a reformer or a slit adsorption method to purify the nitrogen gas. Previously, there were no effective measures for the presence of organic substances such as benzoic acid, p-methyl benzoic acid, phthalic acid, etc., which were present in the venting stream, which would be worthwhile (4) cold gambling gambling and thus to the reformer and The pressure swing adsorption system causes serious blockage of the bed; at the same time, the organic matter present in the exhaust gas flow will have a serious impact on the group of the steel oxide; therefore, the process of direct conversion without the treatment of harmful substances is not feasible. . In addition, the specification of the patent also states that a carbon private reaction can be used to convert carbon monoxide into methane gas to remove carbon monoxide, but in the actual operation remotely, the newly generated gas-burning gas __ will also be used in the The temporary inactivation of Pd_C catalyst affects the normal reaction of the hydrogenation reactor. Further, the hydrogen concentration obtained by the recovery is not guaranteed to meet the requirements of the subsequent processes. SUMMARY OF THE INVENTION An object of the present invention is to provide a method for recovering hydrogen in a gas stream discharged from a phthalic acid plant to solve the above problems in the prior art. The invention removes the acidic substance and the high-boiling and easily crystallized substance in the process gas discharged during the crystallization process of the phthalic acid by domain washing treatment, so that it can be 098116489 Form No. A0101 Page 4 / Total 16 Page 0982027942-0 201041840 [ [0012] [0013] [0016] [0016] The entire application is applied to subsequent processes. The technical solution provided by the present invention is as follows: A method for recovering hydrogen in a discharge gas stream of a phthalic acid plant comprises the following steps: al. maintaining the exhaust gas directly obtained by recrystallizing phthalic acid at 2 〇〇C to 300 °C is washed with a small amount of solvent solution. A2. The exhaust gas directly obtained when recrystallizing phthalic acid is kept at 2〇〇C to 300C with a small amount of alkali solution to reduce the washing process, and the alkali-washed gas is introduced into the reformer; the temperature of the reforming furnace is controlled at 200«> ; c to 3 〇 (rc, pressure 〇 to 4. 6Mpa, catalyzed by a methanol cracking catalyst, the carbon monoxide in the gas is reacted with water vapor to convert hydrogen to produce hydrogen. a3. The exhaust gas directly obtained when recrystallizing the stearic acid remains At 200 ° (: to 3 〇 0 ° (: washing with a small amount of miscellaneous liquid, the gas after shouting treatment is introduced into the reformer; the temperature of the reformer is controlled to 200 ° C to 30 (TC, pressure 0 to 4. 6Mpa introduces methanol vapor into the reformer, catalyzes with methanol cracking catalyst, converts the gas-oxygen and the sulphur gas into reaction with water vapor to produce hydrogen. b. Introduces the exhaust gas after the steps a1 and a2sta3 In the heat exchanger or the cooling tower, the condensable gas is condensed; and the obtained hydrogen-rich gas stream is introduced into the pressure swing adsorption device to remove other impurities in the hydrogen-rich gas stream to obtain a hydrogen concentration of 99.99 wt% or more. Pure hydrogen at a concentration of 5 ppm wt The gas stream is recovered. Among them, the effluent gas obtained directly from the recrystallization of the stearic acid is 098116489. Form No. A0101 Page 5 of 16 0982027942-0 201041840 Carbon monoxide in the body accounts for the total amount of gas other than water 3 When 〇〇〇PPm wt, the process proceeds to step a1 or a3; after detecting, the amount of carbon monoxide in the exhaust gas directly obtained when the bismuth dicarboxylic acid is recrystallized accounts for the total amount of gas other than water > 3000 ppm wt A2 or a3 processes 'where 'al, a2 and a3 are optional ones, venting the gas either through step a to step b; or through steps a2 to b; or through steps a3 to [0017] Alkaline washing can ensure the subsequent operation is normal, excellent
選使用熱碱處理，絕大部分的酸性物質及高沸點易結晶 物質在這一步驟中被輪去。該步驟可以在保持較高的壓 力條件下進入變壓吸附系統，也可以在較低壓力下進入 變壓吸附系統，除去一氧化凌及二氧化碳等雜質，提純 氫氣。最終，經變壓吸附系統純化的氫氣加壓後加入新 鮮氫氣股中，隨之進入氫化反應器中反應。為了保證氫 化反應的品質，應嚴格監控回收氫氣流的棘度，不合格 氣體選擇排放或者重新吸附.處理。 [0018] 一氧化碳與水蒸氣反應轉化為氫氣的反應式如下： (：0 + Ι12〇 = (：〇2+Η2 ’ 一氧化碳的轉化率可達99%。It is treated with hot alkali, and most of the acidic substances and high-boiling, easily crystallized substances are removed in this step. This step can enter the pressure swing adsorption system while maintaining high pressure, or enter the pressure swing adsorption system at a lower pressure to remove impurities such as monoxide and carbon dioxide to purify hydrogen. Finally, the hydrogen purified by the pressure swing adsorption system is pressurized and added to the fresh hydrogen gas, and then enters the hydrogenation reactor for reaction. In order to ensure the quality of the hydrogenation reaction, the toughness of the hydrogen gas stream should be strictly monitored, and the unqualified gas should be discharged or re-adsorbed. [0018] The reaction formula of the reaction of carbon monoxide with water vapor to convert to hydrogen is as follows: (: 0 + Ι 12 〇 = (: 〇 Η Η 2 ′ The conversion rate of carbon monoxide is up to 99%.
[0019] 甲醇與水蒸氣反應轉化為氫氣的反應式如下：ch3〇h+h2〇 = C02 + 3H2。 [0020] 前述回收精笨二甲酸工廠排放氣流中氫氣的方法中，苯 二曱酸為間二笨甲酸、對二甲苯酸或鄰苯二甲酸的至少 一種。 [0021] 前述回收精笨二甲酸工廠排放氣流中氫氣的方法中，碱 098116489 表單煸號A0101 第6頁/共16頁 0982027942-0 201041840 [0022] [0023] ❹ [0024] [0025] Ο [0026] 洗處理用的碱溶液為lwt%〜45wt°/。的NaOH或ΚΟΗ溶液， 碱溶液的壓力略高於排放氣體的壓力，碱溶液的溫度則 應小於或等於排放氣體溫度。碱液的壓力比排放氣體的 壓力略高可保證可以充分地洗滌排放氣體。 前述回收精苯二甲酸工廠排放氣流中氫氣的方法中，碱 洗處理步驟可以在喷霧塔、填料塔或盤式塔中進行。 前述回收精苯二甲酸工廠排放氣流中氫氣的方法中，碱 洗處理步驟前或後還可以包括水洗處理步驟，以預先洗 滌或防止氣體夾帶鹼性液體的鈉、鉀等金屬離子。碱洗 處理可以是多段式處理，以更為徹底地去除其中的酸性 物質及高沸點易結晶物質。 前述回收精苯二曱酸工廠排放氣流中氫氣的方法中，步 驟b中的變壓吸附裝置的壓力操作範圍為0至4Mpa，溫度 範圍 55°C。 前述回收精苯二曱酸工廠排放氣流中氫氣的方法中，所 述排放氣體為H2、一氧化碳、水蒸氣、二氧化碳、醋酸 、苯甲酸、對甲基苯甲酸或微量液滴夾帶的苯二曱酸中 的至少一種。 前述回收精苯二甲酸工廠排放氣流中氫氣的方法中，所 述可凝性氣體為水蒸氣、醋酸、對曱基苯甲酸，苯甲酸 或苯二甲酸中的至少一種。 前述回收精苯二甲酸工廠排放氣流中氫氣的方法中，所 述酸性物質為二氧化碳、笨甲酸、醋酸、曱基苯甲酸或 苯二曱酸等有機物質中的至少一種。 098116489 表單編號A0101 第7頁/共16頁 0982027942-0 [0027] 201041840 [0028] 前述回收精笨二甲酸工廠排放氣流中氫氣的方法中 述甲醇裂解催化劑為銅基催化劑及其他可用催化气。 本發明所提及的精鄰苯二曱酸或精間笨二曱酸生產工蓺 基本與精對笨二甲酸類似，在此不細述^ 在本發明中，術語“略”指的是所討論數值周圍的—個 區間。如本申請中所使用的“略低於χ”表示從叉到乂減X 的10%的區間，優選為從X到X減X的5%的區間；又如本發 明中所使用的“略高於X”表示從X到X加χ的1〇%的區門 優選為從X到X加X的5%的區間。 ... .. ：.. ..... . ·· . 除非特別指名，這裏所使用的所有教術和科學術锌的八 義與本發明所屬技術領域一i技術人員通常所理解的含 義相同。同樣，所有在此提及的出版物、專利申靖 利及其他參考資料均引入本發明作為參考。 專 [〇〇32]本發明可將精苯二曱酸結晶過程中排放的工藝氣 氫氣提高到一定濃度後進行回收，同時減少〜 中的 #r /1 排放量，使其可安全地應用於後續工藝，其適用呶的 精苯二甲酸生產工藝，並可適用於處理回收所有；各積 結晶過程排放的工藝氣體，是一項極具經濟 3氫的 孝 o 價值的氫氣回收方法。由於本發明的排放氣題 長保 化爐、變壓吸附系統前均經過碱洗處理，氣趲中=八轉 醋酸'甲基苯甲酸、苯二甲酸等有機物質岣在3有的 中洗脫，不會在轉化爐及變壓吸附系統形成墦塞，赉綠 ，也不會影響氧化銅等組成的催化劑的催化敦泉同時 【實施方式】 [0029] [0030] [0031] 所 098116489 表單編號A0101 第8頁/共16頁 〇982〇 2794? 201041840 [0033] 通過下面給出的本發明實施例可進一步瞭解本發明，但 本發明的保護範圍不限於此。 [0034] 第一實施例： [0035] 本實施例中的物料量均以重量份數為基準，在待處理的 精對苯二甲酸結晶過程中排放的工藝氣體中，每單位時 間的供給量中，含有氫氣1 000份，C01份，水蒸氣20000 份，C〇24份，苯甲酸0. 5份，對曱基苯甲酸0. 5份和其他 雜質2份，壓力為35 kg/cm2g (表壓），溫度為240°C。 〇 [0036] 將排放氣體送入噴霧塔，用35. 5kg/cm2g、40°C、 7wt%NaOH溶液碱洗處理，氫氧化納〔NaOH〕溶液的壓力 比排放氣體的壓力略高，以保證可以充分地洗滌去除排 放氣體中的酸性物質。經碱溶液充分洗滌後，得到含氫 氣1 000份，一氧化碳1份，水蒸氣8000份，其他雜質2份 的排放氣體。 [0037] 將碱洗處理後的排放氣體送入冷卻塔或換熱器中，將氣 Q 體冷卻至35°C，水蒸氣在其中冷凝下來，再將含氫氣 . 1 000份、一氧化碳1份、其他雜質2份和少量水蒸汽的富 氫氣流引入變壓吸附裝置，得到1 000份含極少量雜質的 純的回收氫氣。純的回收氫氣引入氫化反應器中重新回 收使用。 [0038] 第二實施例： [0039] 本實施例中的物料量均以重量份數為基準，在待處理的 精對苯二甲酸結晶過程中排放的工藝氣體中，每單位時 間的供給量中，含有氫氣100份，一氧化碳15份，水蒸氣 098116489 表單編號A0101 第9頁/共16頁 0982027942-0 201041840 1 000 0份，C〇24份，苯甲酸0. 5份，對甲基苯曱酸0. 8份 和其他雜質1份，壓力為35kg/cm2g (表壓），溫度為 240〇C。 [0040] 將排放氣體送入塔盤式塔，用35. 5kg/cm2g、50°C、 15wt%KaOH溶液域洗處理，NaOH溶液的壓力比排放氣體 的壓力略高，以保證可以充分地洗滌去除排放氣體中的 酸性物質經碱溶液充分洗滌後，得到含氫氣100份，一氧 化碳15份，水蒸氣7500份，其他雜質1份的排放氣體。 [0041] 將碱洗處理後的排放氣體送入壓力為30 kg/cm2g的轉化 爐中，轉化爐溫度控制在200°C至220°C，使用銅系催化 劑催化反應，得到氫氣114份，一氧化碳1份，二氧化碳 14份，其他雜質1份和大量水蒸汽。[0019] The reaction of methanol to steam reaction to hydrogen is as follows: ch3〇h+h2〇 = C02 + 3H2. [0020] In the above method for recovering hydrogen in a flow stream of a fine dicarboxylic acid plant, the phthalic acid is at least one of meta-dicarboxylic acid, p-xylene acid or phthalic acid. [0021] In the foregoing method for recovering hydrogen in a gas stream from a stearic dicarboxylic acid plant, the base 098116489 is nicknamed A0101, page 6 / page 16 0982027942-0 201041840 [0023] [0024] [0025] Ο [ 0026] The alkali solution for the washing treatment is 1 wt% to 45 wt ° /. The NaOH or hydrazine solution, the pressure of the alkali solution is slightly higher than the pressure of the exhaust gas, and the temperature of the alkali solution should be less than or equal to the temperature of the exhaust gas. The pressure of the lye is slightly higher than the pressure of the exhaust gas to ensure that the exhaust gas can be sufficiently washed. In the foregoing method for recovering hydrogen from a gas stream of a phthalic acid plant, the alkali washing treatment step may be carried out in a spray tower, a packed column or a tray column. In the above method for recovering hydrogen from a gas stream in a phthalic acid plant, a water washing step may be included before or after the alkali washing treatment step to preliminarily wash or prevent metal ions such as sodium or potassium from being entrained in the alkaline liquid. The alkaline washing treatment can be a multi-stage treatment to more thoroughly remove the acidic substances and the high-boiling and easily crystallizable substances therein. In the above method for recovering hydrogen from a phthalic acid plant discharge gas stream, the pressure swing adsorption device in step b has a pressure operation range of 0 to 4 MPa and a temperature range of 55 °C. In the foregoing method for recovering hydrogen in a gas stream discharged from a phthalic acid plant, the exhaust gas is H2, carbon monoxide, water vapor, carbon dioxide, acetic acid, benzoic acid, p-methylbenzoic acid or a small amount of benzoic acid entrained in a droplet. At least one of them. In the above method for recovering hydrogen in a gas stream discharged from a terephthalic acid plant, the condensable gas is at least one of steam, acetic acid, p-nonylbenzoic acid, benzoic acid or phthalic acid. In the above method for recovering hydrogen from a gas stream in a phthalic acid plant, the acidic substance is at least one of an organic substance such as carbon dioxide, benzoic acid, acetic acid, mercaptobenzoic acid or benzoic acid. 098116489 Form No. A0101 Page 7 of 16 0982027942-0 [0027] The aforementioned method for recovering hydrogen from a stream of a distillate dicarboxylic acid plant is described as a copper-based catalyst and other available catalytic gases. The production process of the precise o-phthalic acid or the adipic acid of the present invention is basically similar to that of the p-dicarboxylic acid, and is not described in detail herein. In the present invention, the term "slightly" refers to the Discuss the interval around the value. "Slightly lower than χ" as used in the present application means a section from the cross to 10% of X minus X, preferably a range of 5% from X to X minus X; and as used in the present invention A value higher than X" means that 1% of the area from X to X is preferably a range of 5% from X to X plus X. ..... :.. ..... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . the same. Also, all publications, patents, and other references mentioned herein are hereby incorporated by reference. Special [〇〇32] The invention can recover the process gas discharged from the phthalic acid crystallization process to a certain concentration, and reduce the #r /1 emission of ~ medium, so that it can be safely applied The subsequent process is applicable to the production process of phthalic acid, and can be applied to the treatment and recovery of all; the process gas discharged from each crystallization process is a hydrogen recovery method with a high economical value of 3 hydrogen. Since the venting gas of the present invention is subjected to an alkali washing treatment before the pressure-increasing furnace and the pressure swing adsorption system, the organic matter such as eight-transacetic acid 'methylbenzoic acid, phthalic acid, etc. in the gas enthalpy is eluted in three. Catalysts that do not form clogging, greening, or affecting the composition of copper oxide and the like in the reformer and the pressure swing adsorption system are simultaneously [embodiment] [0029] [0031] 098116489 Form No. A0101 Page 8 of 16 〇982〇2794? 201041840 [0033] The present invention can be further understood by the embodiments of the present invention given below, but the scope of the present invention is not limited thereto. [0034] First Embodiment: [0035] The amount of material in this embodiment is based on the parts by weight, and the amount of supply per unit time in the process gas discharged during the crystallization of the purified terephthalic acid to be treated. 1份, containing hydrogen, 1 000 parts, C01 parts, water vapor 20,000 parts, C 〇 24 parts, benzoic acid 0.5 parts, p-nonyl benzoic acid 0.5 parts and other impurities 2 parts, pressure 35 kg / cm2g ( Gauge), temperature is 240 ° C. 〇[0036] The exhaust gas is sent to the spray tower, and alkali treated with 35.5 kg/cm2g, 40 ° C, and 7 wt% NaOH solution, and the pressure of the sodium hydroxide [NaOH] solution is slightly higher than the pressure of the exhaust gas to ensure The acidic substance in the exhaust gas can be sufficiently washed and removed. After sufficiently washing with the alkali solution, 1 000 parts of hydrogen gas, 1 part of carbon monoxide, 8000 parts of water vapor, and 2 parts of other impurities are obtained. [0037] The alkali-washed exhaust gas is sent to a cooling tower or a heat exchanger, the gas Q body is cooled to 35 ° C, water vapor is condensed therein, and then hydrogen is contained. 1 000 parts, 1 part of carbon monoxide The hydrogen-rich stream of 2 parts of other impurities and a small amount of water vapor is introduced into the pressure swing adsorption device to obtain 1 000 parts of pure recovered hydrogen gas containing a very small amount of impurities. The pure recovered hydrogen is introduced into the hydrogenation reactor for reuse. [0038] Second Embodiment: [0039] The amount of material in this embodiment is based on the parts by weight, and the amount of supply per unit time in the process gas discharged during the crystallization of the purified terephthalic acid to be treated. Medium, containing 100 parts of hydrogen, 15 parts of carbon monoxide, water vapor 098116489 Form No. A0101 Page 9 of 16 pages 0982027942-0 201041840 1 000 0 parts, C 〇 24 parts, benzoic acid 0.5 parts, p-methyl benzoquinone The acid was 0.8 parts and 1 part of other impurities, the pressure was 35 kg/cm2g (gauge pressure), and the temperature was 240 〇C. [0040] The exhaust gas is sent to the tray tray, and washed with 35. 5 kg / cm 2 g, 50 ° C, 15 wt% KaOH solution, the pressure of the NaOH solution is slightly higher than the pressure of the exhaust gas to ensure sufficient washing After the acidic substance in the exhaust gas is sufficiently washed with the alkali solution, 100 parts of hydrogen, 15 parts of carbon monoxide, 7500 parts of water vapor, and 1 part of other impurities are obtained. [0041] The alkali-washed exhaust gas is sent to a reforming furnace having a pressure of 30 kg/cm 2 g, and the temperature of the reforming furnace is controlled at 200 ° C to 220 ° C, and a copper-based catalyst is used to catalyze the reaction to obtain 114 parts of hydrogen, carbon monoxide. 1 part, 14 parts of carbon dioxide, 1 part of other impurities and a large amount of water vapor.
[0042] 將轉化後的排放氣體送入冷卻塔中，將氣體冷卻至5(TC ，水蒸氣在其中冷凝下來，再將含氫氣11 4份、二氧化碳 14份、一氧化碳1份和其他雜質1份和少量水蒸汽的富氫 氣流引入變壓吸附裝置，得到114份含極少量雜質的純的 回收氫氣。純的回收氫氣引入氫化反應器中重新回收使 用。 [0043] 第三實施例： [0044] 本實施例中的物料量均以重量份數為基準，在待處理的 精對苯二曱酸結晶過程中排放的工藝氣體中，每單位時 間的供給量中，含有氫氣50份，一氧化碳15份，水蒸氣 1 000 0份，二氧化碳9份，苯甲酸0. 5份，對曱基苯曱酸 0. 2份，其他雜質0. 5份，壓力為35kg/cm2g (表壓）， 098116489 表單編號A0101 第10頁/共16頁 0982027942-0 201041840 [0045] [0046] 〇 [0047] Ο [0048] 溫度為240°C。 將排放氣體送入塔盤式塔，用35. 5kg/cm2g ' 4(TC、 15wt%NaOH溶液域洗處理，NaOH溶液的壓力比排放氣體 的壓力略高’以保證可以充分地洗滌去除排放氣體酸性 物質。經充分碱洗洗滌後，得到含氫氣50份，一氧化碳 15份’水蒸氣7500份，其他雜質〇. 5份的排放氣體。 喊洗處理後的氣體引入壓力為3〇 kg/cm2g的轉化爐中， 轉化爐溫度控制在280°C〜300。〇，向其中加入50份的甲 醇蒸汽，用銅系催化劑催化，將氣髏中的一氧化碳、甲 醇與水蒸氣反應轉化為氫氣，得到含有氫氡2u. 5份， COO. 5份，水蒸氣7435. 5份，二氧化碳63. 5扮，曱醇1 份’其他雜質0· 5份的排放氣體^ 將轉化後的排放氣體送入的冷卻塔中，將氣體冷卻至35 °c，水蒸氣和甲醇在其中冷凝下來，再將含氫氣2115份 、一氧化碳0. 5份、二氧化碳63. 5份和少鲞水蒸氣的富氫 氣流引入變壓吸附裝置，得到2115份含極少量其他雜質 的純的回收氫氣。再將純的回收氫氣引入氫化反應器中 使用。 上述實施例為本發明較佳的實施方式，但本發明的實施 方式並不受上述實_的限制，其他的任何未背離本發 明的精神實質與原理下所作的改變、修佛 '替代、組合 、簡化’均應為等效的置換方式，都包含在本發明的保 護範圍之内。 【圖式簡單說明】 098116489 表單編號A0101 第11頁/共16頁 0982027942-0 201041840 [0049] 無 【主要元件符號說明】 [0050] 無 098116489 表單編號A0101 第12頁/共16頁 0982027942-0[0042] The converted exhaust gas is sent to a cooling tower, and the gas is cooled to 5 (TC, water vapor is condensed therein, and then 14 parts of hydrogen, 14 parts of carbon dioxide, 1 part of carbon monoxide, and 1 part of other impurities. The hydrogen-rich stream with a small amount of water vapor is introduced into the pressure swing adsorption device to obtain 114 parts of pure recovered hydrogen containing a very small amount of impurities. The pure recovered hydrogen is introduced into the hydrogenation reactor for reuse. [0043] Third embodiment: [0044] The amount of material in this embodiment is based on the parts by weight, and in the process gas discharged during the crystallization of the purified terephthalic acid to be treated, 50 parts of hydrogen per unit time is supplied, and carbon monoxide 15 is contained.份份, the water vapor is 1 000 parts, the carbon dioxide is 9 parts, the benzoic acid is 0.5 parts, the p-nonyl benzoic acid is 0.2 parts, the other impurities are 0.5 parts, the pressure is 35kg/cm2g (gauge pressure), 098116489 No. A0101, page 10 / page 16 0982027942-0 201041840 [0045] [0047] 温度 [0047] Ο [0048] The temperature is 240 ° C. The exhaust gas is sent to the tray tower, with 35. 5kg / cm2g ' 4 (TC, 15wt% NaOH solution domain washing treatment, pressure ratio of NaOH solution The pressure of the gas is slightly higher to ensure that the exhaust gas acid substance can be sufficiently washed and washed. After sufficient alkali washing and washing, 50 parts of hydrogen gas, 15 parts of carbon monoxide '7500 parts of water vapor, and other impurities 〇. 5 parts of exhaust gas are obtained. After the shouting treatment, the gas is introduced into a reforming furnace with a pressure of 3 〇kg/cm2g, and the temperature of the reforming furnace is controlled at 280 ° C to 300. 〇, 50 parts of methanol vapor is added thereto, and the gas is catalyzed by a copper catalyst. The carbon monoxide, methanol and steam in the hydrazine are converted into hydrogen to obtain hydroquinone 2u. 5 parts, COO. 5 parts, water vapor 7435. 5 parts, carbon dioxide 63. 5 dress, sterol 1 part 'other impurities 0 · 5份的碳碳, 2, 5%, carbon dioxide, carbon dioxide, carbon dioxide, carbon dioxide, carbon dioxide, carbon dioxide, carbon dioxide 63. The hydrogen-rich stream of 5 parts and less water vapor is introduced into the pressure swing adsorption device to obtain 2115 parts of pure recovered hydrogen gas containing a very small amount of other impurities, and the pure recovered hydrogen gas is introduced into the hydrogenation reactor for use. The present invention is not limited to the above-described embodiments, and any other changes, modifications, substitutions, Equivalent replacement means are included in the scope of protection of the present invention. [Simple description of the drawing] 098116489 Form No. A0101 Page 11 of 16 0982027942-0 201041840 [0049] No [Main component symbol description 】 [0050] No 098116489 Form No. A0101 Page 12 / Total 16 Page 0982027942-0