TW583018B

TW583018B - Method for removing a volatile component from a high viscosity liquid by using rotation pack bed

Info

Publication number: TW583018B
Application number: TW91109050A
Authority: TW
Inventors: Sheng Yang; Chia-Chang Lin; I-Min Tseng; Wen-Tzong Liu; Hua-Tang Yu
Original assignee: Ind Tech Res Inst
Priority date: 2002-04-30
Filing date: 2002-04-30
Publication date: 2004-04-11

Abstract

A high viscosity liquid is fed into a rotation pack bed at a position with a distance far enough from a rotation axis, creating a centrifugal force exerted on the high viscosity liquid overwhelms a drag thereof, so that it can flow radially through the rotation pack bed. A high pressure gas is introduced into the rotation pack bed peripherally and/or a suction force source is connected to a position near the rotation axis, so that a volatile component contained in the high viscosity fluid is entrained in the gas counter currently flowing through the rotation pack bed and exiting from the position near the axis, or the volatile component part exits from the position near the axis in gas phase, and thus the volatile component is removed from the high viscosity liquid. A second liquid can also be fed into the rotation pack bed to react with the high viscosity liquid, so that a reaction product is formed, and a volatile side product is removed at the same time.

Description

583018 A7 B7 五、發明説明（1 ) 發明領域本發明係關於一種利用質傳設備，尤其是旋轉塡充床，從高黏度液體中移除其中所含的揮發成分的方法。發明背景三芳基氧膦（triarylphosphites)抗氧化劑P(〇Ar)3是塑膠加工常用的添加劑，其中Ar代表芳基。傳統方法包含化學反應與脫除副產物等兩個步驟，分別說明該兩步驟程序如下：化學反應步驟：於批式攪拌槽中加入ArOH液體並持續攪拌，再徐徐加入PC13液體，所進行之化學反應爲如式（1)、式（2)、式（3) 所示之平衡反應。583018 A7 B7 V. Description of the invention (1) Field of the invention The present invention relates to a method for removing volatile components contained in a high-viscosity liquid by using mass transfer equipment, especially a rotary radon packed bed. BACKGROUND OF THE INVENTION The triarylphosphites antioxidant P (0Ar) 3 is an additive commonly used in plastic processing, where Ar represents an aryl group. The traditional method includes two steps: chemical reaction and removal of by-products. The two steps are described separately as follows: Chemical reaction step: ArOH liquid is added to a batch stirred tank and continuously stirred, and then PC13 liquid is added slowly. The reaction is an equilibrium reaction represented by formula (1), formula (2), and formula (3).

ArOH + PC13 ArOPCl2 +HC1 (1)ArOH + PC13 ArOPCl2 + HC1 (1)

ArOH + ArOPCl2 — — (ArO)2PCl +HC1 (2)ArOH + ArOPCl2 — — (ArO) 2PCl + HC1 (2)

ArOH + (ArO)2PCl (ArO)3P +HC1 (3) 式（1)、式（2)、式（3)中之副產品HC1是具可揮發性之氣體，該HC1氣體使得攪拌反應槽中之黏稠反應液體產生大量泡沬而易溢出槽體，以致於批式攪拌槽無法連續快速進料，而導致每批次處理4公噸所需之反應滯留時間要長達1 0小時以上。脫除副產物步驟：在化學反應步驟所產生之副產物HC1必須自反應系統脫除，使反應破壞平衡而提高抗氧化劑ρ(〇α〇3的產率。傳本紙張尺度適用中國國家標準（CNS ) A4規格（2ΚΓΧ%7公釐） (請先閱讀背面之注意事項再填寫本頁) 訂經濟部智慧財產局員工消費合作社印製 58301^ 經濟部智慧財產局員工消費合作社印製 A7 B7五、發明説明（2 ) .統方法脫除HC1是先在常壓下使用情性氣體吹除至酸値爲 3 mgKOH/g，再抽真空及通入惰性氣體脫除至酸値爲0.1 mgKOH/g止。要脫除HC1至一般市場可接受之酸値爲0.1 mgKOH/g之產品，所須耗費之時間長達12小時以上。 1974 年 Herzog 及 Hoppe (USP 3,823,207)揭示了一種製備三芳基氧膦抗氧化劑的方法，其中將傳統使用攪拌槽之批次製程，改成以淺盤加隔板所形成之溢流式反應槽之連續式製程。該溢流隔板所形成反應區的面積與體積之比値較傳統攪拌槽大。當反應流體通過溢流隔板時，可形成較大之面積與體積比，有利於反應物接觸並脫除HC1氣體。另外於反應液中加入不與PC13反應之高沸點溶劑以降低反應液之黏稠性。藉以上之改善措施，使進料之投料速率得以增大，雖然反應滯留時間較傳統方法縮短，但是仍然需要長達1小時，而且所外加之溶劑必須進行蒸餾程序分離，大幅增加能源消耗量。發明槪要本發明的一主要目的在於提供一種利用旋轉塡充床，從高黏度液體中移除其中所含的揮發成分的方法。本發明的另一目的，在於提供一種利用旋轉塡充床來進行一高黏度液體反應物與另一流體的反應，及同時脫除揮發性副產物來製備一產物的方法。本發明將高黏度液體進料到旋轉塡充床的一離軸心足夠遠的位置，利用離軸心較遠處的離心力較大的原理，使 -5 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁) •lifrArOH + (ArO) 2PCl (ArO) 3P + HC1 (3) The by-product HC1 in formula (1), formula (2), and formula (3) is a volatile gas, and the HC1 gas makes the The viscous reaction liquid generates a lot of bubbles and easily overflows the tank, so that the batch stirred tank cannot continuously and quickly feed, resulting in a reaction retention time of more than 10 hours required for processing 4 metric tons per batch. Step of removing by-products: The by-product HC1 produced in the chemical reaction step must be removed from the reaction system, so that the reaction breaks the balance and improves the yield of the antioxidant ρ (〇α〇3. It is said that the paper size applies to Chinese national standards ( CNS) A4 specification (2KΓ ×% 7mm) (Please read the precautions on the back before filling out this page) Order printed by the Intellectual Property Bureau Employee Consumption Cooperative of the Ministry of Economy 58301 ^ Printed by the Intellectual Property Bureau Employee Consumption Cooperative of the Ministry of Economic Affairs A7 B7 Five 2. Description of the invention (2). The conventional method for removing HC1 is to blow off the acid tritium to 3 mgKOH / g with atmospheric gas under normal pressure, and then vacuum and inert gas to remove the acid tritium to 0.1 mgKOH / g. It takes more than 12 hours to remove HC1 to a product that is generally accepted as 0.1 mgKOH / g acidic acid on the market. Herzog and Hoppe (USP 3,823,207) in 1974 revealed a method for preparing triaryl oxygen. The method of phosphine antioxidant, wherein the batch process using the conventional stirring tank is changed to a continuous process of an overflow reaction tank formed by adding a shallow plate and a partition plate. The area of the reaction zone formed by the overflow partition plate and Volume ratio It is larger than the traditional stirring tank. When the reaction fluid passes through the overflow baffle, it can form a larger area to volume ratio, which is conducive to the contact of the reactants and the removal of HC1 gas. In addition, the reaction solution is added with a high boiling point that does not react with PC13 Solvent to reduce the viscosity of the reaction solution. With the above improvement measures, the feed rate can be increased. Although the reaction retention time is shorter than the traditional method, it still takes up to 1 hour, and the additional solvent must be distilled. The program is separated, and the energy consumption is greatly increased. SUMMARY OF THE INVENTION A main object of the present invention is to provide a method for removing a volatile component contained in a high-viscosity liquid by using a rotary radon packed bed. Another object of the present invention, The purpose is to provide a method of using a rotary packed bed to perform a reaction between a highly viscous liquid reactant and another fluid, and to simultaneously remove a volatile by-product to prepare a product. The present invention feeds a high-viscosity liquid to a rotary packed bed The position of the bed is far enough from the center of the bed, using the principle of larger centrifugal force farther from the center of the bed, so that -5 Use Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page) • lifr

、1T 583018 經濟部智慧財產局員工消費合作社印製 A7 B7, 1T 583018 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7

五、發明説明G 該高黏度液體順利徑向流過該旋轉塡充床。圖不之簡單說明圖一爲一適合用於本發明的多液型旋轉塡充床反應系統的剖面示意圖。圖號說明 1.帶動馬達 2.傳動軸心 .第一進料口 7·分散盤 8.氣體出口 9.液體出口 10.氣體入口 11.密封裝置 12.機械軸封 1 3 .內循環泵 1 4.內循環管路 1 5 .回流比控制閥發明詳細說明一種用於使兩不同比重的流體以逆流方式接觸來進行質量傳送（mass transfer)的設備已爲業界所知悉，例如美國專利第 4283255; 4382045; 4382900;及 4400275。中國專利公開號CN 111 6 1 46 A( 1 9%年）提出使用該質傳設備的超細顆粒的製備方法，其中多相物流由同心套管的內、外管經分佈器進料至一旋轉塡充床的軸心位置，通過旋轉重力場作用，在塡充床中接觸並進行反應。美國專利第60485 1 3 號（2〇00年）發展出一種利用旋轉塡充床製備次鹵酸 (hyp ohalous acid)之方法，將一種液體反應物與氯氣流經高速旋轉塡充床，作逆流式接觸進行反應，並使氣、液分離。該製程同時包含吸附、反應及脫附，可以用比傳統製程少本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)V. Description of the invention G The highly viscous liquid flows smoothly through the rotary pumped bed. Brief Description of the Drawings Fig. 1 is a schematic cross-sectional view of a multi-liquid type rotary packed bed reaction system suitable for the present invention. Explanation of drawing number 1. Drive motor 2. Transmission shaft center. First feed inlet 7 · Dispersion disk 8. Gas outlet 9. Liquid outlet 10. Gas inlet 11. Sealing device 12. Mechanical shaft seal 1 3. Internal circulation pump 1 4. Internal circulation pipeline 15. The invention of the return ratio control valve is described in detail. A device for mass transfer by contacting two fluids with different specific gravity in countercurrent manner is known in the industry, for example, US Patent No. 4283255 4382045; 4382900; and 4400275. Chinese Patent Publication No. CN 111 6 1 46 A (19% years) proposes a method for preparing ultrafine particles using the mass transfer device, in which a multi-phase stream is fed from an inner tube and an outer tube of a concentric sleeve to a The axis position of the rotary radon filling bed is contacted and reacted in the radon filling bed by the action of the rotating gravity field. U.S. Patent No. 60485 1 3 (2000) developed a method for preparing hypo ohalous acid by using a rotary rhenium packed bed. A liquid reactant and chlorine gas flow were passed through a high-speed rotary rhenium packed bed for countercurrent. The reaction is carried out by contact, and the gas and liquid are separated. This process also includes adsorption, reaction and desorption, which can be used less than the traditional process. The paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling this page)

3 .塡充床 6.第二進料口 4.轉鼓經濟部智慧財產局員工消費合作社印製 A7 __B7五、發明説明（4 ) 5 0%的較低氣體流量，使產率由傳統製程的80%提高到旋轉塡充床製程的90%。前述中國專利公開號CN 111 6 1 46 A及美國專利第6〇48 5 Π號的液體進料的黏度均很小約只有〗cp (25它），因此由旋轉塡充床的軸心位置進料，該液體進料仍然可受到足夠的旋轉重力場作用而徑向流過該塡充床。在前述發明背景所描述的p(oa〇3抗氧化劑的製備方法中，我們認爲克服HC1在黏稠反應液之質傳限制是縮短製造程序、提高抗氧化劑ρ(οα〇3產率、降低抗氧化劑 ρ(οα〇3酸値的關鍵因素。因此我們想到使用旋轉塡充床來促進HC1在黏稠反應液之質傳速率，但是該高黏度ArOH液體，若如習知技藝被進料到旋轉塡充床的軸心位置處，該高黏度ArOH液體會因黏度的關係滯留在該處、無法徑向流過該旋轉塡充床。爲了解決此問題，我們發明了一新型旋轉塡充床，其中一適於該高黏度液體進料的進料口被設置在離軸心一足夠遠的位置，以產生足夠的離心力促使該高黏度液體徑向流過該旋轉塡充床。藉由此項思考模式，我們同時提出從高黏度液體中移除其中所含的揮發成分的方法，例如從高黏度聚胺基甲酸酯中除去未反應的多異氰酸酯單體，及從高黏度三壬基苯氧膦（tris nonylphenol phosphite)抗氧化劑中除去氯化氫。依據本發明內容所完成的一種用旋轉塡充床從高黏度液體中移除所含的揮發成分的方法，包含下列步驟： a)將一高黏度液體導入一繞一軸心旋轉中的旋轉塡充床，該旋轉塡充床係位於一艙（housing)內，該旋轉塡充床 (請先閱讀背面之注意事項再填寫本頁)3. 塡 Filling bed 6. Second feed port 4. Drum printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 __B7 V. Description of the invention (4) Lower gas flow of 50%, so that the yield is controlled by traditional processes 80% increase to 90% of the rotary radon filling process. The aforementioned Chinese Patent Publication No. CN 111 6 1 46 A and US Patent No. 6048 5 Π both have a viscosity of only about cp (25), so they are fed from the axis position of the rotary concrete filling bed. Material, the liquid feed can still be subjected to a sufficient rotating gravity field to flow radially through the packed bed. In the method for preparing p (oa〇3) antioxidants described in the foregoing background of the invention, we believe that overcoming the mass transfer limitation of HC1 in viscous reaction solutions is to shorten the manufacturing process, increase the yield of antioxidants ((αα3), reduce the antioxidant The key factor of the oxidizing agent ρ (οα〇3 acid). Therefore, we thought of using a rotating rhenium packed bed to promote the mass transfer rate of HC1 in the viscous reaction solution. At the axis position of the packed bed, the highly viscous ArOH liquid will stay there due to the viscosity and cannot flow through the rotary concrete filling bed radially. In order to solve this problem, we have invented a new type of rotary concrete filling bed, of which A feeding port suitable for the feeding of the high-viscosity liquid is set at a position far enough from the center of the axis to generate sufficient centrifugal force to cause the high-viscosity liquid to flow radially through the rotary packed bed. With this consideration Mode, we also propose methods to remove volatile components from high viscosity liquids, such as removing unreacted polyisocyanate monomers from high viscosity polyurethanes, and Tris nonylphenol phosphite removes hydrogen chloride from antioxidants. A method for removing volatile components from high-viscosity liquids using a rotary hydrazone packed bed completed in accordance with the present invention includes the following steps: a) a High-viscosity liquid is introduced into a rotating concrete filling bed which is rotating around an axis. The rotating concrete filling bed is located in a housing. The rotating concrete filling bed (please read the precautions on the back before filling this page)

本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 583018 A7 B7 i、發明説明（5 ) 具有圍繞軸心的一中央通道區及圍繞該中央通道區的環形塡充區，該環形塡充區內被固定有塡充物，並且該環形塡充區與該中央通道區只通過兩者之界面呈流體相通，且該環形塡充區與該艙只通過該環形塡充區的外圓周呈流體相通，其中該高黏度液體被導入在該環形塡充區的一位置，使得該高黏度液體在該位置受到足夠大的離心力而可以從該位置往遠離該軸心方向徑向流過該塡充物； b) 將一高壓氣體由接近該環形塡充區的外圓周的一位置，導入該旋轉塡充床及/或使該中央通道區連接於一吸力來源，使得該高黏度液體在徑向流過該塡充物時，該高黏度液體中所含的一揮發成分連同該高壓氣體，或該揮發成分本身以氣相方式，由該中央通道區流出該旋轉塡充床及該艙；及 c) 於該艙底部收集從該環形塡充區的外圓周流出的被純化的液體。適用於本發明方法的步驟a)的該高黏度液體於室溫具有一小於3 0 00 cps的黏度。較佳的，步驟a)的該高黏度液體包含三壬基苯氧膦（tris nonylphenol phosphite)及氯化氫，其中該氯化氫以氣相方式由該中央通道區流出該旋轉塡充床及該艙，及一氯化氫含量降低的三壬基苯氧膦液體於該艙的底部被收集。較佳的，步驟a)的該高黏度液體包含聚胺基甲酸酯及未反應的多異氰酸酯單體，其中該多異氰酸酯單體以氣相方式由該中央通道區流出該旋轉塡充床及該艙，及多異氰本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閱讀背面之注意事項再填寫本頁)This paper size applies to China National Standard (CNS) A4 (210X297 mm) 583018 A7 B7 i. Description of the invention (5) A central channel area around the axis and a circular filling area surrounding the central channel area, the ring shape The filling material is fixed in the filling area, and the annular filling area and the central channel area are in fluid communication only through the interface between the two, and the annular filling area and the cabin only pass through the outside of the annular filling area. The circumference is in fluid communication, wherein the high-viscosity liquid is introduced at a position in the annular filling area, so that the high-viscosity liquid receives sufficient centrifugal force at the position to flow radially from the position away from the axis. The filling; b) introducing a high-pressure gas from a position close to the outer circumference of the annular filling area into the rotating filling bed and / or connecting the central channel area to a suction source so that the highly viscous liquid A volatile component contained in the high-viscosity liquid together with the high-pressure gas, or the volatile component itself flows out of the rotary hydration filling bed from the central channel region when flowing through the hydration filling in a radial direction. And the tank; and c) collecting at the bottom of the tank the purified liquid flowing from the outer circumference of the annular charging zone. The highly viscous liquid suitable for use in step a) of the method of the present invention has a viscosity of less than 3,000 cps at room temperature. Preferably, the high-viscosity liquid of step a) includes tris nonylphenol phosphite and hydrogen chloride, wherein the hydrogen chloride flows out of the rotary aerated bed and the cabin from the central channel region in a gas phase manner, and Trinonylphenoxyphosphine liquid with reduced hydrogen chloride content was collected at the bottom of the tank. Preferably, the high-viscosity liquid of step a) comprises polyurethane and unreacted polyisocyanate monomer, wherein the polyisocyanate monomer flows out of the rotary packed bed from the central channel region in a gas phase manner and The size of this compartment and the polyisocyanate paper are applicable to the Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

、1T 經濟部智慧財產局員工消費合作社印製 583018 A7 _______B7_ 五、發明説明（6 ) 酸酯單體含量降低的聚胺基甲酸酯液體於該艙的底部被收集。 (請先閲讀背面之注意事項再填寫本頁) 較佳的，於步驟b)—高壓氮氣被導入於該艙內作爲該高壓氣體。較佳的，本發明方法進一步包含將步驟c)的被純化的液體的一部份回流至步驟a)及導入該環形塡充區。較佳的，於步驟b)—高壓氣體被導入於該艙內，及該高黏度液體在徑向流過該塡充物時，與該高壓氣體接觸並產生化學反應，其中該化學反應的一部份產物，連同該高壓氣體以氣相方式由該中央通道區流出該旋轉塡充床及該艙，及該化學反應的另一部份產物與未反應的該高黏度液體於該艙的底部被收集。經濟部智慧財產局員工消費合作社印製較佳的，步驟a)進一步包含將一液態反應物由該中央通道區導入該旋轉塡充床，該液態反應物受到離心力而往遠離該軸心方向徑向流過該塡充物，且該液態反應物與該高黏度液體產生化學反應，其中該化學反應的一部份產物，以氣相方式由該中央通道區流出該旋轉塡充床及該艙，及該化學反應的另一部份產物與未反應的該高黏度液體及該液態反應物於該艙的底部被收集。更佳的，於步驟 b)—惰性氣體被導入於該艙內作爲該高壓氣體，該化學反應的一部份產物，連同該高壓惰性氣體以氣相方式由該中央通道區流出該旋轉塡充床及該艙，及該化學反應的另一部份產物與未反應的該高黏度液體及該液態反應物於該艙的底部被收集。例如該高黏度液體包含壬基酚’該液態反本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）經濟部智慧財產局員工消費合作社印製 583018 A7 ____ B7 五、發明説明（7 ) 應物包含三氯膦（PC13)，該高壓情性氣體爲氮氣，該化學反應的一產物爲氯化氫，它以氣相方式連同氮氣由該中央通道區流出該旋轉塡充床，及該化學反應的另一產物爲三壬基苯氧膦（tris nonylphenol phosphite)其與未反應的壬基酚及三氯膦於該艙的底部被收集。一適合用於本發明的多液型旋轉塡充床反應系統，如圖一所示，包含一帶動馬達1、傳動軸心2、帶動含有網狀塡充物的塡充床3、轉鼓4。二種液體分別由第一進料口 5，及第二進料口6，噴入塡充床中。第一進料口 5之液料進入分散盤7分成極細液滴，與第二進料口 6之液料由離心力帶動一同進入塡充床3，於其中充分接觸而進行反應。反應所產生氣體副產物由氣體出口 8排出，其中該出口 8設支管接抽氣裝置（未示於圖中）以建立本反應系統之真空環境。液體產物則由本體外殼16收集，而由液體出口 9排出。當含有氣體副產物之反應液，由第一進料口 5、第二進料口 6進入旋轉塡充床3時，利用惰性氣體如氮氣、二氧化碳、氬氣或其他不參與反應之氣體，由氣體入口 10進入旋轉塡充床3，於其中與液料液逆流接觸，帶走氣體副產物，由氣體出口 8排出。爲防止惰性氣體旁路至該氣體出口 8流失，設置密封裝置Π，其採用迷宮式密封。一機械軸封12被設置於該傳動軸心2上，以防止由系統內部壓力與外部壓力差所產生的洩漏。爲使反應物能有更多接觸機會，設一內循環泵13及內循環管路1 4以及回流比控制閥1 5。 ____- 10 -_ 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） (請先閲讀背面之注意事項再填寫本頁)Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs of the 1T 583018 A7 _______B7_ V. Description of the Invention (6) Polyurethane liquid with reduced acid ester monomer content was collected at the bottom of the cabin. (Please read the notes on the back before filling out this page) Preferably, in step b) —high pressure nitrogen is introduced into the cabin as the high pressure gas. Preferably, the method of the present invention further comprises refluxing a portion of the purified liquid of step c) to step a) and introducing it into the annular charging zone. Preferably, in step b), a high-pressure gas is introduced into the cabin, and when the high-viscosity liquid flows radially through the filling, it contacts the high-pressure gas and generates a chemical reaction, wherein one of the chemical reactions is Part of the product, together with the high-pressure gas, flows out of the rotary bed and the cabin in a gas phase from the central channel area, and another part of the chemical reaction and the unreacted high-viscosity liquid are at the bottom of the cabin. Be collected. The consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints better. Step a) further includes introducing a liquid reactant from the central channel area into the rotary concrete filling bed. The liquid reactant is subjected to centrifugal force and moves away from the axis. Flowing through the filling material, and the liquid reactant reacts with the high-viscosity liquid, and a part of the product of the chemical reaction flows out of the rotating filling bed and the cabin from the central channel area in a gas phase manner And another part of the chemical reaction product and the unreacted high viscosity liquid and the liquid reactant are collected at the bottom of the chamber. More preferably, in step b)-an inert gas is introduced into the cabin as the high-pressure gas, and a part of the product of the chemical reaction, together with the high-pressure inert gas, flows out of the rotary charge from the central channel region in a gas phase manner. The bed and the chamber, and another part of the chemical reaction product and the unreacted high-viscosity liquid and the liquid reactant are collected at the bottom of the chamber. For example, the high-viscosity liquid contains nonylphenol. The liquid anti-paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm). Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 583018 A7 ____ B7 V. Description of the invention (7 The reactant contains trichlorophosphine (PC13), the high-pressure emotional gas is nitrogen, and a product of the chemical reaction is hydrogen chloride, which flows out of the rotary packed bed in the gas phase together with nitrogen from the central channel region, and the chemical Another product of the reaction was tris nonylphenol phosphite, which was collected with unreacted nonylphenol and trichlorophosphine at the bottom of the cabin. A multi-liquid rotary radon filling bed reaction system suitable for the present invention, as shown in FIG. 1, includes a driving motor 1, a driving shaft center 2, a radon filling bed 3 including a reticulated radon filling, and a rotating drum 4. . The two liquids are sprayed into the packed bed from the first feeding port 5 and the second feeding port 6, respectively. The liquid material in the first feed port 5 enters the dispersion plate 7 and is divided into extremely fine droplets. The liquid material in the second feed port 6 is driven into the packed bed 3 by centrifugal force, and is fully contacted to perform the reaction. The gas by-products produced by the reaction are discharged from a gas outlet 8, wherein the outlet 8 is provided with a branch pipe connected to an extraction device (not shown in the figure) to establish a vacuum environment of the reaction system. The liquid product is collected by the body casing 16 and discharged through the liquid outlet 9. When the reaction liquid containing gaseous by-products enters the rotary packed bed 3 from the first feed port 5 and the second feed port 6, an inert gas such as nitrogen, carbon dioxide, argon or other gases not participating in the reaction is used. The gas inlet 10 enters the rotary concrete filling bed 3, where it comes into countercurrent contact with the liquid material liquid, takes away the gas by-products, and is discharged from the gas outlet 8. In order to prevent the inert gas from being bypassed to the gas outlet 8, the sealing device Π is provided, which adopts a labyrinth seal. A mechanical shaft seal 12 is provided on the transmission shaft center 2 to prevent leakage caused by the pressure difference between the internal pressure of the system and the external pressure. In order to make the reactants have more contact opportunities, an internal circulation pump 13 and an internal circulation pipeline 14 and a reflux ratio control valve 15 are provided. ____- 10 -_ This paper size applies to China National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back before filling this page)

583018 A7 _____B7五、發明説明（8 ) 藉由下述數個實施例以進一步說明本發明之內容、目的、及特徵，惟應注意這些實施例僅係用於說明而非侷限本發明之範圍。實施例 1 - 3 : TNPP (Tris nonylphenol phosphite)批次式脫除 HC1 旋轉塡充床之塡充床規格爲：內徑76 mm，外徑160 mm，厚度33 mm，塡充床轉速固定於1300 rpm，以氮氣爲脫氣劑。TNPP進料口位置在離塡充床軸心5 cm處。取TNPP 5kg，其酸値爲0.18 mgKOH/g，及黏度爲1000 cps。改變 TNPP之進料溫度、氮氣與TNPP之氣、液比，其所得到之結果如表一所示。由測試結果可以發現，經旋轉塡充床處理15 min (—個循環）後之酸値降爲0.06〜0.08 mgKOH/g。再繼續循環處理至45min之後（共三個循環）後，該TNPP之酸値降爲 0.04 〜0.06 mgKOH/g。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局8工消費合作社印製表1 實施例 1 2 3 進料酸値 mgKOH/g 0.18 0.18 0.18 15min出料酸値 mgKOH/g 0.08 0.06 0.07 45min出料酸値 mgKOH/g 0.06 0.05 0.04 進料溫度 °C 130 170 150 進液量 mL/min 200 200 200 進氣量 L/min 15 15 20 氣液比 75 75 100 轉速 rpm 1300 1300 1300 _- 11 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 583018 A7 ___B7__ 五、發明説明（9 ) 實施例4: TNPP連續式脫除HC1 旋轉塡充床規格爲：內徑120 mm，外徑600 mm，厚度 100 mm。塡充床轉速固定於1200 rpm。TNPP進料口位置離塡充床軸心5 cm處。氮氣溫度爲88 °C，氮氣流量爲1250 Ι/min。TNPP之黏度爲 1〇〇〇 cps，溫度爲 114°C，TNPP流量爲25 1/min，經塡充床處理前之酸値0.3 mgKOH/g，經旋轉塡充床脫除後之酸値降爲0.16 mgKOH/g。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 ___- 12 - 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐）583018 A7 _____B7 V. Description of the Invention (8) The following embodiments are used to further explain the content, purpose, and features of the present invention, but it should be noted that these embodiments are only for illustration and not to limit the scope of the present invention. Example 1-3: TNPP (Tris nonylphenol phosphite) batch removal of HC1 rotary concrete filling bed The specifications of the concrete filling bed are: inner diameter 76 mm, outer diameter 160 mm, thickness 33 mm, and the speed of the filling bed is fixed at 1300 rpm, using nitrogen as a degassing agent. The TNPP feed inlet was located 5 cm away from the axis of the filling bed. Take 5kg of TNPP, its acid hydrazone is 0.18 mgKOH / g, and its viscosity is 1000 cps. The results obtained by changing the feed temperature of TNPP and the gas and liquid ratio of nitrogen to TNPP are shown in Table 1. From the test results, it can be found that the acid tritium decreased to 0.06 ~ 0.08 mgKOH / g after 15 minutes (-cycle) of the rotary tritium filling bed treatment. After the cycle treatment was continued to 45 minutes (three cycles in total), the acid content of the TNPP was reduced to 0.04 to 0.06 mgKOH / g. (Please read the precautions on the back before filling this page) Printed by the 8th Industrial Cooperative Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Example 1 2 3 Feed acid 値 mgKOH / g 0.18 0.18 0.18 15min Output acid 値 mgKOH / g 0.08 0.06 0.07 45min output acid mgKOH / g 0.06 0.05 0.04 Feed temperature ° C 130 170 150 Feed volume mL / min 200 200 200 Air intake L / min 15 15 20 Gas-liquid ratio 75 75 100 Speed rpm 1300 1300 1300 _- 11-This paper size is in accordance with Chinese National Standard (CNS) A4 (210X297 mm) 583018 A7 ___B7__ 5. Description of the invention (9) Example 4: TNPP continuous removal of HC1 Rotary concrete filling bed Specifications: inner diameter 120 mm, outer diameter 600 mm, thickness 100 mm.塡 The speed of the packed bed is fixed at 1200 rpm. The position of the TNPP feed inlet is 5 cm from the axis of the bed. The nitrogen temperature was 88 ° C and the nitrogen flow was 1250 Ι / min. TNPP has a viscosity of 1000 cps, a temperature of 114 ° C, and a TNPP flow rate of 25 1 / min. The acid before treatment with a packed bed is 0.3 mgKOH / g, and the acid is removed after removal with a rotary packed bed. 0.16 mgKOH / g. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ___- 12-This paper size applies to China National Standard (CNS) A4 (210X297 mm)

Claims

583018583018

種用旋轉塡充床從高黏度液體中移除所含的揮發成分的方法，包含下列步驟： a) 將一高黏度液體導入一繞一軸心旋轉中的旋轉塡充床，該旋轉塡充床係位於一艙（housing)內，該旋轉塡充床具有圍繞軸心的一中央通道區及圍繞該中央通道區的環形塡充區，該環形塡充區內被固定有塡充物，並且該環形塡充區與該中央通道區只通過兩者之界面呈流體相通，且該環形塡充區與該艙只通過該環形塡充區的外圓周呈流體相通，其中該高黏度液體被導入在該環形塡充區的一位置，使得該高黏度液體在該位置受到足夠大的離心力而可以從該位置往遠離該軸心方向徑向流過該塡充物； b) 將一高壓氣體由接近該環形塡充區的外圓周的一位置，導入該旋轉塡充床及/或使該中央通道區連接於一吸力來源，使得該高黏度液體在徑向流過該塡充物時，該高黏度液體中所含的一揮發成分連同該高壓氣體，或該揮發成分本身以氣相方式由該中央通道區流出該旋轉塡充床及該艙；及 c) 於該艙底部收集從該環形塡充區的外圓周流出的被純化的液體。 2. 如申請專利範圍第1項的方法，其中步驟a)的該高黏度液體於室溫具有一小於3000 cps的黏度。 3. 如申請專利範圍第1項的方法，其中步驟a)的該高黏度液體包含三壬基苯氧膦（tris nonylphenol phosphite)及氯化 -13 - 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） (請先閱讀背面之注意事項再填寫本頁) •P ;線- 經濟部智慧財產局員工消費合作社印製 583018 A8 D8___(2003年5月絛正) 六、申請專利範圍氫，其中該氯化氫以氣相方式由該中央通道區流出該旋轉塡充床及該艙，及一氯化氫含量降低的三壬基苯氧膦液體於該艙的底部被收集。 4·如申請專利範圍第1項的方法，其中步驟a)的該高黏度液體包含聚胺基甲酸酯及未反應的多異氰酸酯單體，其中該多異氰酸酯單體以氣相方式由該中央通道區流出該旋轉塡充床及該艙，及多異氰酸酯單體含量降低的聚胺基甲酸酯液體於該艙的底部被收集。 5·如申請專利範圍第1項的方法，其中於步驟b)—高壓氮氣被導入於該艙內作爲該高壓氣體。 6·如申請專利範圍第1項的方法，其進一步包含將步驟c) 的被純化的液體的一部份回流至步驟a)及導入該環形塡充區。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 14- 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）A method for removing a volatile component from a high-viscosity liquid using a rotary vacuum filling bed, comprising the following steps: a) introducing a high-viscosity liquid into a rotary vacuum filling bed rotating around an axis, the rotary vacuum filling The bed is located in a housing, and the rotary filling bed has a central channel area around the axis and a circular filling area surrounding the central channel area, the filling material is fixed in the circular filling area, and The annular charging region and the central channel region are in fluid communication only through the interface between the two, and the annular charging region and the capsule are in fluid communication with each other only through the outer circumference of the annular charging region, wherein the high-viscosity liquid is introduced At a position in the annular filling region, the highly viscous liquid is subjected to sufficient centrifugal force at the position to flow radially through the filling from the position away from the axis; b) passing a high-pressure gas from A position close to the outer circumference of the annular filling area, when the rotating filling bed is introduced and / or the central channel area is connected to a suction source, so that the highly viscous liquid flows radially through the filling, the High viscosity fluid A volatile component contained in the high-pressure gas, or the volatile component itself flows out of the rotary charging bed and the cabin from the central passage area in a gas phase manner; and c) is collected from the annular charging area at the bottom of the cabin Purified liquid flowing from the outer circumference of the 2. The method according to item 1 of the patent application, wherein the high viscosity liquid of step a) has a viscosity of less than 3000 cps at room temperature. 3. The method according to item 1 of the patent application scope, wherein the high viscosity liquid of step a) comprises tris nonylphenol phosphite and chlorinated -13-Chinese paper standard (CNS) A4 applies to this paper size Specifications (210 χ 297 mm) (Please read the notes on the back before filling out this page) • P; Line-Printed by the Employee Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 583018 A8 D8___ (June 2003) 6. Application The scope of the patent is hydrogen, in which the hydrogen chloride flows out of the rotary bed and the cabin in a gaseous manner from the central channel area, and a trinonylphenoxyphosphine liquid with reduced hydrogen chloride content is collected at the bottom of the cabin. 4. The method of claim 1, wherein the high-viscosity liquid of step a) comprises polyurethane and unreacted polyisocyanate monomer, wherein the polyisocyanate monomer is passed from the center in a gas phase manner. The channel area flows out of the rotary bed and the cabin, and the polyurethane liquid with reduced polyisocyanate monomer content is collected at the bottom of the cabin. 5. The method according to item 1 of the patent application scope, wherein in step b)-high pressure nitrogen is introduced into the cabin as the high pressure gas. 6. The method according to item 1 of the patent application scope, further comprising returning a part of the purified liquid in step c) to step a) and introducing the annular filling area. (Please read the precautions on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 14- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)