TW201502086A

TW201502086A - Pure plant waste water purification and recycle

Info

Publication number: TW201502086A
Application number: TW103117387A
Authority: TW
Inventors: Finbar Gerald Mcdonnell; Ronojoy Goho; Kristan James Wadrop
Original assignee: Invista Tech Sarl
Priority date: 2013-05-20
Filing date: 2014-05-16
Publication date: 2015-01-16
Also published as: WO2014189786A1

Abstract

The invention is related to methods for purifying aqueous waste streams from a pure terephthalic acid (PTA) manufacturing plant and recycling of the purified water back into the PTA plant. The invention also relates to novel aqueous waste stream and purified water stream compositions.

Description

純工廠廢水純化及回收 Purification and recycling of pure factory wastewater

本發明係關於純化來自純對苯二甲酸(PTA)製造工廠之水性廢物流及將經純化水回收返回PTA工廠中之方法。本發明亦關於新穎水性廢物流及經純化水流組合物。 The present invention relates to a process for purifying an aqueous waste stream from a pure terephthalic acid (PTA) manufacturing plant and recycling the purified water back to the PTA plant. The invention also relates to novel aqueous waste streams and purified water stream compositions.

廣泛生產聚(對苯二甲酸伸乙酯)(PET)樹脂且其用於例如飲料及食品容器、熱成形應用、織物中及用作工程樹脂。PET為基於單體單元雙-β-羥基對苯二甲酸酯之聚合物，該單體單元一般由乙二醇及對苯二甲酸(或對苯二甲酸二甲酯)形成。一般而言，必須合成對苯二甲酸(1,4-苯二甲酸)以用作反應物。作為用於PET生產之反應物所需的對苯二甲酸為稱為「經純化對苯二甲酸」(PTA)之形式的對苯二甲酸，其一般含有超過99.99重量%之對苯二甲酸及小於25ppm之4-羧基苯甲醛(4-CBA)。 Poly(terephthalate terephthalate) (PET) resins are widely produced and used in, for example, beverage and food containers, thermoforming applications, fabrics, and as engineering resins. PET is a polymer based on a monomer unit of bis-β-hydroxy terephthalate, which is generally formed of ethylene glycol and terephthalic acid (or dimethyl terephthalate). In general, terephthalic acid (1,4-phthalic acid) must be synthesized for use as a reactant. The terephthalic acid required as a reactant for PET production is terephthalic acid in the form of "purified terephthalic acid" (PTA), which generally contains more than 99.99% by weight of terephthalic acid and Less than 25 ppm of 4-carboxybenzaldehyde (4-CBA).

在商業規模上，一般以兩階段製程製備適用於PET生產之經純化對苯二甲酸(PTA)，該製程包含對二甲苯氧化繼而純化粗氧化產物。首先，氧化(例如使用空氣)對二甲苯，得到粗對苯二甲酸(CTA)，諸如描述於例如Saffer等人之美國專利第2,833,816號中，該專利以引用的方式併入本文中。一般在包含脂族羧酸(例如乙酸)之溶劑中且在金屬催化劑(例如鈷或錳鹽或化合物)存在下進行氧化反應。 On a commercial scale, purified terephthalic acid (PTA) suitable for PET production is typically prepared in a two-stage process comprising oxidation of p-xylene followed by purification of the crude oxidation product. First, the p-xylene is oxidized (e.g., using air) to give crude terephthalic acid (CTA), such as described in U.S. Patent No. 2,833,816, issued to, et al. The oxidation reaction is generally carried out in a solvent comprising an aliphatic carboxylic acid such as acetic acid and in the presence of a metal catalyst such as a cobalt or manganese salt or a compound.

隨後純化藉由此氧化反應得到的粗對苯二甲酸，因其通常受諸如4-羧基苯甲醛、對甲苯甲酸之雜質及多種賦予對苯二甲酸淡黃色顏色之有色雜質污染。除至少一種物理程序(例如結晶、洗滌等)之外，純化CTA通常還需要至少一種化學轉化。一種常見化學轉化為氫化CTA，其可將CTA中之主要雜質中之一者4-羧基苯甲醛轉化成較易於移除之對甲苯甲酸。因此，一般將CTA溶解於水中且在第VIII族貴金屬氫化催化劑(例如負載的鉑或鈀催化劑)存在下對其進行氫化作為純化之第一步驟。藉由一或多種物理程序回收經純化對苯二甲酸。舉例而言，一般藉助於將產物自水結晶獲得PTA，因為大部分雜質(包括對甲苯甲酸、乙酸)及少量對苯二甲酸保留在溶液中。可藉由諸如過濾或離心之方式回收PTA且洗滌，得到純所需物質。剩餘溶液稱為「純工廠母液」(PPML)。 Subsequently, the crude terephthalic acid obtained by the oxidation reaction is purified because it is usually subjected to Such as 4-carboxybenzaldehyde, p-toluic acid impurities and a variety of colored impurities that impart a pale yellow color of terephthalic acid. In addition to at least one physical procedure (eg, crystallization, washing, etc.), purifying CTA typically also requires at least one chemical transformation. One common chemical conversion to hydrogenated CTA converts 4-carboxybenzaldehyde, one of the major impurities in CTA, to p-toluic acid, which is easier to remove. Thus, CTA is typically dissolved in water and hydrogenated in the presence of a Group VIII noble metal hydrogenation catalyst (e.g., supported platinum or palladium catalyst) as the first step of purification. The purified terephthalic acid is recovered by one or more physical procedures. For example, PTA is generally obtained by crystallization of the product from water, as most of the impurities (including p-toluic acid, acetic acid) and a small amount of terephthalic acid remain in solution. The PTA can be recovered and washed by filtration or centrifugation to obtain a pure desired material. The remaining solution is referred to as "pure factory mother liquor" (PPML).

得到經純化對苯二甲酸後剩餘之PPML一般包含一定濃度之雜質。儘管在商業規模上PPML可經處理以作為流出水釋放，但可有利地對其進行純化及回收以用於生產更多對苯二甲酸。此外，雜質通常包括可經回收且純化之粗對苯二甲酸以及易於轉化成對苯二甲酸之對甲苯甲酸。此稱為純工廠母液溶劑萃取(PPMLSX)。來自PPMLSX之水性溶離液不適合於不經進一步處理而在PTA工廠內直接回收或直接供應至基於逆滲透(RO)之技術(諸如通常用於使水去鹽之技術)。 The PPML remaining after obtaining purified terephthalic acid generally contains a certain concentration of impurities. Although PPML can be treated on a commercial scale for release as effluent water, it can be advantageously purified and recovered for use in the production of more terephthalic acid. Further, the impurities generally include crude terephthalic acid which can be recovered and purified, and p-toluic acid which is easily converted into terephthalic acid. This is called pure factory mother liquor solvent extraction (PPMLSX). Aqueous dispersions from PMLLSX are not suitable for direct recovery or direct supply to reverse osmosis (RO) based technologies (such as those commonly used to desalinate water) without further processing.

水控制為全球範圍內所有工業之日益增長的問題，尤其在缺少淡水的區域中。目前，大部分PTA工廠以「貫流」模式使用去礦物質水進行產物純化。「貫流」意謂幾乎不採用水回收；其中該製程中所用水之大部分作為液體流出物排出。與控制水相關之成本逐漸增加且藉由採用更佳水回收技術；可減少PTA工廠之總體操作成本同時使其更加環保。 Water control is a growing problem for all industries worldwide, especially in areas where fresh water is scarce. Currently, most PTA plants use demineralized water for product purification in a "cross-flow" mode. "Through flow" means that water recovery is hardly used; most of the water used in the process is discharged as liquid effluent. The costs associated with controlling water are increasing and by using better water recovery technologies; the overall operating costs of PTA plants can be reduced while making them more environmentally friendly.

PPMLSX製程可回收大部分來自PPML之有機酸。在進行此操作時，該製程產生水性廢物流與氧化與純化製程步驟之水性輸出之大部分的組合，其回收將提供潛在環境及經濟益處。由PPMLSX製程產生之水性流體不適合於在PTA工廠中直接回收，因為其含有某些可溶性有機酸及金屬鹽以及懸浮有機酸固體。另外，PPMLSX製程之較佳操作溫度範圍與前述雜質之存在的組合意謂該流體不能藉由直接供應至基於習知已知去鹽膜技術之RO單元的進料流而滿意地處理。溫度與組合物之此組合將導致不能藉由RO製程充分移除溶解之酸及乙酸且可能引起有機酸對RO膜之結垢污染與由溶解之金屬鹽及懸浮固體所致的RO膜積垢。 The PPMLSX process recovers most of the organic acids from PPML. Doing this At the time, the process produces a combination of a large portion of the aqueous waste stream and the aqueous output of the oxidation and purification process steps, the recovery of which will provide potential environmental and economic benefits. Aqueous fluids produced by the PMLLSX process are not suitable for direct recovery in PTA plants because they contain certain soluble organic acids and metal salts as well as suspended organic acid solids. Additionally, the combination of the preferred operating temperature range of the PPLLSX process with the presence of the aforementioned impurities means that the fluid cannot be satisfactorily processed by direct supply to a feed stream based on a conventional RO unit of known desalting membrane technology. This combination of temperature and composition will result in the inability to adequately remove dissolved acid and acetic acid by the RO process and may cause fouling of the RO membrane by organic acids and fouling of RO membranes by dissolved metal salts and suspended solids. .

因此，宜提供可移除金屬鹽、溶解之酸及懸浮固體之RO前製程步驟。該(該等)步驟將允許使用PPMLSX流程中之習知RO製程，進而藉由增加潔淨水之輸出且降低操作成本而使得PTA工廠更加環保。 Therefore, it is desirable to provide a pre-RO process step for removing the metal salt, the dissolved acid, and the suspended solids. This (these) steps will allow the use of the conventional RO process in the PMLLSX process, which in turn will make the PTA plant more environmentally friendly by increasing the output of clean water and reducing operating costs.

在本發明之一個態樣中，提供一種處理由純工廠母液溶劑萃取製程產生之水性溶離流體的方法，其包含：藉由使水性流體與鹼接觸來提高水性流體之pH以形成pH調節流體；使pH調節流體與過濾器接觸以形成經處理流體；及使經處理流體與逆滲透單元接觸以形成去礦物質水流。用鹼提高水性流體之pH將可溶性金屬鹽轉化成不溶性化合物，同時亦將可溶性與不溶性有機酸轉化成相應酸鹽。過濾器可為標準超濾膜，其移除不溶性金屬化合物及其他剩餘不溶性組分。逆滲透單元移除有機酸鹽(包括鈉鹽)，同時平衡pH。 In one aspect of the invention, a method of treating an aqueous dissolved fluid produced by a pure plant mother liquor solvent extraction process, comprising: increasing a pH of an aqueous fluid to form a pH adjusting fluid by contacting an aqueous fluid with a base; The pH adjusting fluid is contacted with the filter to form a treated fluid; and the treated fluid is contacted with a reverse osmosis unit to form a demineralized water stream. The pH of the aqueous fluid is increased with a base to convert the soluble metal salt to an insoluble compound, while also converting the soluble and insoluble organic acid to the corresponding acid salt. The filter can be a standard ultrafiltration membrane that removes insoluble metal compounds and other remaining insoluble components. The reverse osmosis unit removes the organic acid salt (including the sodium salt) while balancing the pH.

在本發明之另一態樣中，提供一種使用獲自純工廠母液溶劑萃取製程之去礦物質水流的方法，其包含：藉由使由純工廠母液溶劑萃取製程產生之水性流體與鹼接觸來提高該水性流體的pH以形成pH調節流體；使pH調節流體與過濾器接觸以形成經處理流體；使經處理流體與逆滲透單元接觸以形成去礦物質水流；及輸送去礦物質流體至PTA工廠中之其他製程。其他製程可包括粗對苯二甲酸結晶、晶體水洗滌、對苯二甲酸純化、蒸餾、分離及蒸汽產生。 In another aspect of the invention, there is provided a method of using a demineralized water stream obtained from a pure plant mother liquor solvent extraction process, comprising: contacting an aqueous fluid produced by a pure plant mother liquor solvent extraction process with a base Increasing the pH of the aqueous fluid to form a pH adjusting fluid; contacting the pH adjusting fluid with a filter to form a treated fluid; contacting the treated fluid with a reverse osmosis unit to form a demineralized water stream; and delivering the demineralized fluid to the PTA Other processes in the factory. Other processes may include crude terephthalic acid crystals, crystal water Washing, purification of terephthalic acid, distillation, separation and steam generation.

在本發明之另一態樣中，提供一種在由純工廠母液溶劑萃取製程產生之水性溶離流體中將有機酸轉化成酸鹽之方法，其包含：使水性溶離流體與鹼接觸，其中水性溶離流體在與鹼接觸前具有約600ppm至約5000ppm之有機酸濃度。 In another aspect of the invention, there is provided a method of converting an organic acid to an acid salt in an aqueous dissolved fluid produced by a pure plant mother liquor solvent extraction process, comprising: contacting an aqueous dissolved fluid with a base, wherein the aqueous dissolution The fluid has an organic acid concentration of from about 600 ppm to about 5000 ppm prior to contact with the base.

在本發明之另一態樣中，提供一種自pH為至少8之水性流體移除氫氧化鈷及氫氧化錳之方法，其包含：使水性流體與過濾器接觸，其中水性流體在與過濾器接觸前具有約500ppm至約2000ppm之鈉濃度。 In another aspect of the invention, a method of removing cobalt hydroxide and manganese hydroxide from an aqueous fluid having a pH of at least 8 is provided, comprising: contacting an aqueous fluid with a filter, wherein the aqueous fluid is in contact with the filter The sodium concentration is from about 500 ppm to about 2000 ppm prior to contacting.

在本發明之甚至另一態樣中，提供一種自pH為至少8之水性流體移除鈉鹽之方法，其包含：使水性流體與逆滲透單元接觸，其中水性流體在與逆滲透單元接觸前具有小於0.1ppm之鈷濃度及約500ppm至約3000ppm之乙酸鹽濃度。 In an even further aspect of the invention, a method of removing a sodium salt from an aqueous fluid having a pH of at least 8 is provided, comprising: contacting an aqueous fluid with a reverse osmosis unit, wherein the aqueous fluid is in contact with the reverse osmosis unit There is a cobalt concentration of less than 0.1 ppm and an acetate concentration of from about 500 ppm to about 3000 ppm.

在本發明之另一態樣中，提供一種純工廠母液溶劑萃取水性溶離流體，其包含：約600ppm至約3000ppm之濃度的乙酸；約50ppm至約450ppm之濃度的對苯二甲酸；及在自約0.1ppm至約50ppm之濃度的金屬，其中水性溶離流體之pH係小於5。 In another aspect of the present invention, there is provided a pure plant mother liquor solvent extraction aqueous dissolved fluid comprising: acetic acid at a concentration of from about 600 ppm to about 3000 ppm; terephthalic acid at a concentration of from about 50 ppm to about 450 ppm; A metal having a concentration of from about 0.1 ppm to about 50 ppm, wherein the aqueous system has a pH system of less than 5.

在本發明之另一態樣中，提供一種水性流體，其包含：約500ppm至約2000ppm之鈉鹽及約0.05ppm至約50ppm之濃度的金屬氫氧化物，其中水性流體之pH為至少8。 In another aspect of the invention, an aqueous fluid is provided comprising: from about 500 ppm to about 2000 ppm of a sodium salt and from about 0.05 ppm to about 50 ppm of a metal hydroxide, wherein the aqueous fluid has a pH of at least 8.

在本發明之另一態樣中，提供一種水性流體，其包含：約0至約0.1ppm之鈷；及約0至約0.1ppm之錳，其中水性流體之pH為至少8。 In another aspect of the invention, an aqueous fluid is provided comprising: from about 0 to about 0.1 ppm cobalt; and from about 0 to about 0.1 ppm manganese, wherein the aqueous fluid has a pH of at least 8.

在本發明之另一態樣中，提供一種潔淨水流，其包含：約0.5ppm至約20ppm之濃度的乙酸及約0.1ppm至約10ppm之濃度的鈉，其中水流具有約6至約8之pH且實質上不含K、Mg、Ca、Co、Fe及Mn。 In another aspect of the invention, a clean water stream is provided comprising: acetic acid at a concentration of from about 0.5 ppm to about 20 ppm and sodium at a concentration of from about 0.1 ppm to about 10 ppm, wherein the water stream has a pH of from about 6 to about 8 It does not substantially contain K, Mg, Ca, Co, Fe and Mn.

10‧‧‧混合器 10‧‧‧ Mixer

20‧‧‧傾析器 20‧‧‧ Decanter

25‧‧‧熱交換器 25‧‧‧ heat exchanger

30‧‧‧蒸餾塔/塔 30‧‧‧Distillation tower/tower

40‧‧‧冷凝器 40‧‧‧Condenser

50‧‧‧冷凝器 50‧‧‧Condenser

60‧‧‧再沸器 60‧‧‧ reboiler

65‧‧‧熱交換器 65‧‧‧ heat exchanger

70‧‧‧回收塔/塔 70‧‧‧Recycling tower/tower

100‧‧‧中和器 100‧‧‧ neutralizer

110‧‧‧儲料槽 110‧‧‧ hopper

120‧‧‧超濾單元/單元 120‧‧‧Ultrafiltration unit/unit

130‧‧‧逆滲透單元/單元 130‧‧‧Reverse Osmosis Unit/Unit

140‧‧‧第二逆滲透單元/單元 140‧‧‧Second reverse osmosis unit/unit

A‧‧‧PPML流/流體 A‧‧‧PPML flow/fluid

B‧‧‧流體 B‧‧‧ fluid

C‧‧‧流體 C‧‧‧ fluid

D‧‧‧冷凝物流/流體 D‧‧‧ Condensate / Fluid

E‧‧‧混合流體 E‧‧‧ mixed fluid

F1‧‧‧有機流體 F1‧‧‧Organic fluid

F2‧‧‧有機流體/流體 F2‧‧‧Organic fluids/fluids

G‧‧‧流體 G‧‧‧ fluid

J1‧‧‧流體/熱乙酸流體 J1‧‧‧ Fluid/Hot Acetic Acid Fluid

K1‧‧‧水性流體 K1‧‧‧aqueous fluid

K2‧‧‧水性流體/水相流體 K2‧‧‧aqueous fluid/aqueous fluid

L1‧‧‧流出水 L1‧‧‧ outflow water

L2‧‧‧流體 L2‧‧‧ fluid

M‧‧‧流體 M‧‧‧ fluid

P‧‧‧經處理流體 P‧‧‧ treated fluid

Q‧‧‧去礦物質水流 Q‧‧‧Demineral water flow

Q1‧‧‧去礦物質水流 Q1‧‧‧Demineral water flow

Q2‧‧‧去礦物質流體 Q2‧‧‧Demineralized fluid

R1‧‧‧第一通滲透物 R1‧‧‧ first pass permeate

R2‧‧‧滲透物 R2‧‧‧ Penetrant

圖1為本發明之PPML純化系統(PPMLSX系統)之步驟的示意性製程圖，該PPML由PTA生產產生。 Figure 1 is a schematic process diagram of the steps of a PPML purification system (PPMLSX system) of the present invention produced by PTA production.

圖2為本發明之例示性PPMLSX水性流體純化系統之步驟的示意性製程圖，該PPML由PTA生產產生。 2 is a schematic process diagram of the steps of an exemplary PMLLSX aqueous fluid purification system of the present invention produced by PTA production.

現在將在下文中參考附圖更加全面地描述本發明，其中顯示本發明之一些但非所有實施例。實際上，此等發明可以多種不同形式實施，且不應理解為受本文所闡述實施例限制；相反地，提供此等實施例以使得本發明符合適用法定要求。全文之類似符號指類似元件。除非上下文另外明確指示，否則如本說明書中及隨附申請專利範圍中所用之單數形式「一(a)」、「一(an)」、「該」包括複數指示物。 The invention will now be described more fully hereinafter with reference to the accompanying drawings in which FIG. In fact, the invention may be embodied in a variety of different forms and should not be construed as being limited to the embodiments set forth herein; rather, the embodiments are provided so that the invention conforms to the applicable legal requirements. Like symbols throughout the text refer to like elements. The singular forms "a", "an", "the" and "the" are used in the <RTI ID=0.0> </ RTI> </ RTI> <RTIgt;

本發明提供生產經純化對苯二甲酸(PTA)之系統及方法。更特定言之，本發明提供純化在純工廠母液(PPML)純化期間產生之純工廠母液溶劑萃取(PPMLSX)水性溶離流體之系統及方法，該純工廠母液在PTA生產期間產生。美國申請案第61/720675號提供PPMLSX製程之例示性描述，該案以全文引用的方式併入本文中。簡言之，下文描述PPMLSX製程及PTA製程。 The present invention provides systems and methods for producing purified terephthalic acid (PTA). More specifically, the present invention provides systems and methods for purifying a pure plant mother liquor solvent extraction (PPMLSX) aqueous dissolved fluid produced during the purification of pure plant mother liquor (PPML) which is produced during PTA production. An exemplary description of the PMLLSX process is provided in U.S. Application Serial No. 61/720, the entire disclosure of which is incorporated herein by reference. In short, the PMLLSX process and PTA process are described below.

PTA之商業生產通常以液相氧化對伸苯基化合物開始以得到粗(亦即不純)對苯二甲酸。最常用的對伸苯基化合物為對二甲苯(paraxylene/p-xylene)；然而，可使用在伸苯基之對位具有可氧化形成羧基之取代基的任何伸苯基。舉例而言，伸苯基上之例示性取代基可包括(但不限於)甲基、乙基、丙基、異丙基、甲醯基、乙醯基及其組合。取代基可相同或不同。 Commercial production of PTA typically begins with liquid phase oxidation of the pendant phenyl compound to give crude (i.e., impure) terephthalic acid. The most commonly used para-phenylene compound is paraxylene/p-xylene; however, any phenyl group having a substituent which is oxidizable to form a carboxyl group at the para position of the phenyl group can be used. For example, exemplary substituents on the phenyl extending group can include, but are not limited to, methyl, ethyl, propyl, isopropyl, decyl, ethenyl, and combinations thereof. The substituents may be the same or different.

氧化反應中所用之溶劑可改變，但一般包含乙酸，其可視情況含有水。氧化反應可在任何可獲得氧氣的條件下進行。舉例而言，反應可在空氣中(其中空氣中之氧氣可充當氧化劑)及/或在富含純氧氣之環境(例如全氧氣氛圍或添加有一定濃度氧氣之惰性氣體氛圍)中進行。通常使用過渡金屬催化劑及視情況選用之共催化劑。氧化催化劑可改變，且在一些實施例中可包含重金屬鹽或化合物(例如含鈷、錳、鐵、鉻及/或鎳化合物或鹽或其組合)，如例如描述於Saffer等人之美國專利第2,833,816號中，該專利以引用的方式併入本文中。亦可添加多種共催化劑及/或促進劑，包括(但不限於)含溴化合物、溴化鹽、酮(例如丁酮、三乙醯基甲烷、2,3-戊二酮、甲基乙基酮、乙醯基丙酮或其組合)、金屬紫質、鋯鹽或其組合。 The solvent used in the oxidation reaction may vary, but generally comprises acetic acid, which may optionally contain water. The oxidation reaction can be carried out under any conditions in which oxygen can be obtained. For example, the reaction can be in air (where oxygen in the air can act as an oxidant) and/or in pure oxygen-rich The environment (for example, a full oxygen atmosphere or an inert gas atmosphere to which a certain concentration of oxygen is added) is carried out. Transition metal catalysts and, if appropriate, cocatalysts are generally employed. The oxidation catalyst can vary, and in some embodiments can comprise heavy metal salts or compounds (e.g., containing cobalt, manganese, iron, chromium, and/or nickel compounds or salts, or combinations thereof), such as, for example, the U.S. patent described in Saffer et al. This patent is incorporated herein by reference in its entirety. A variety of co-catalysts and/or promoters may also be added, including but not limited to bromine-containing compounds, bromide salts, ketones (eg, methyl ethyl ketone, triethyl decyl methane, 2,3-pentanedione, methyl ethyl) Ketone, ethenylacetone or a combination thereof, metallic violet, zirconium salt or a combination thereof.

氧化通常在高溫及/或高壓下進行。一般而言，溫度及壓力必須足以確保氧化反應進行，且亦確保溶劑之至少一部分維持液相。因此，一般需要在高溫與高壓條件下進行氧化反應。氧化反應所需之溫度可隨催化劑及視情況選用之共催化劑及/或促進劑之選擇而變化。在某些實施例中，反應溫度係在約160℃至約220℃範圍內；然而，在一些實施例中，溫度可維持低於160℃同時仍獲得氧化產物。 Oxidation is usually carried out at elevated temperatures and/or pressures. In general, the temperature and pressure must be sufficient to ensure that the oxidation reaction proceeds, and that at least a portion of the solvent is maintained in the liquid phase. Therefore, it is generally required to carry out an oxidation reaction under high temperature and high pressure conditions. The temperature required for the oxidation reaction can vary depending on the choice of catalyst and, if desired, cocatalyst and/or promoter. In certain embodiments, the reaction temperature is in the range of from about 160 °C to about 220 °C; however, in some embodiments, the temperature can be maintained below 160 °C while still obtaining an oxidation product.

在氧化反應之後，通常冷卻反應混合物(例如藉由在降低之壓力下傳送混合物至一或多個結晶器單元)。所得混合物一般包含可自其中分離粗對苯二甲酸之漿液。分離粗對苯二甲酸之方式可改變，且可包含過濾、離心及或任何其他適合之分離固相及液相之方式。通常用淡水及/或乙酸洗滌固相，得到粗對苯二甲酸之經分離晶體。在一些實施例中，液相(通常包含水、乙酸、乙酸甲酯及多種其他組分)可經處理以使得乙酸與水及其他低沸點組分分離。舉例而言，在一些實施例中，將液相汽化且傳送蒸汽至蒸餾設備(例如，在該設備中其可進行共沸蒸餾)。一般而言，共沸蒸餾可為使乙酸與水分離之有效方法，且在有機共沸添加劑存在下進行。通常，在共沸蒸餾設備內，將形成底部產物，其主要包含乙酸(在一些實施例中，可將其回收至氧化反應中)。頂部產物可包含有機共沸添加劑、水及乙酸甲酯，且隨後可經冷卻以形成冷凝物。 After the oxidation reaction, the reaction mixture is typically cooled (e.g., by transferring the mixture to one or more crystallizer units under reduced pressure). The resulting mixture generally comprises a slurry from which crude terephthalic acid can be separated. The manner in which the crude terephthalic acid is separated can vary and can include filtration, centrifugation, and or any other suitable means of separating the solid phase from the liquid phase. The solid phase is usually washed with fresh water and/or acetic acid to obtain a separated crystal of crude terephthalic acid. In some embodiments, the liquid phase (typically comprising water, acetic acid, methyl acetate, and various other components) can be treated to separate the acetic acid from water and other low boiling components. For example, in some embodiments, the liquid phase is vaporized and steam is delivered to a distillation apparatus (eg, in which the azeotropic distillation can be performed). In general, azeotropic distillation can be an effective method for separating acetic acid from water and is carried out in the presence of an organic azeotrope additive. Typically, in an azeotropic distillation apparatus, a bottom product will be formed which will primarily comprise acetic acid (in some embodiments, it can be recovered to the oxidation reaction). The top product may comprise an organic azeotrope additive, water and methyl acetate, and It can then be cooled to form a condensate.

隨後純化粗對苯二甲酸，得到適用於生產聚(對苯二甲酸伸乙酯)之PTA。在此階段多種雜質一般存在於粗對苯二甲酸中。舉例而言，4-羧基苯甲醛為最常見污染物中之一者，以及賦予粗對苯二甲酸一定程度之顏色的化合物。除至少一種物理程序(例如結晶、洗滌等)之外，CTA之純化通常還需要至少一種化學轉化。化學轉化可包括多種製程，包括(但不限於)催化加氫處理、催化處理、氧化處理及/或再結晶。商業上，最常用化學轉化為氫化，其可將CTA主要雜質中之一者(4-羧基苯甲醛)轉化成較易於移除之對甲苯甲酸。 The crude terephthalic acid is subsequently purified to give a PTA suitable for the production of poly(terephthalate). A variety of impurities are generally present in the crude terephthalic acid at this stage. For example, 4-carboxybenzaldehyde is one of the most common contaminants and a compound that imparts a degree of color to crude terephthalic acid. In addition to at least one physical procedure (e.g., crystallization, washing, etc.), purification of CTA typically requires at least one chemical transformation. Chemical conversion can include a variety of processes including, but not limited to, catalytic hydrotreating, catalytic processing, oxidation processing, and/or recrystallization. Commercially, the most common chemical conversion to hydrogenation converts one of the major CTA impurities (4-carboxybenzaldehyde) to p-toluic acid which is easier to remove.

根據本發明可使用多種氫化條件。一般將CTA溶解於溶劑(例如水)中。在一些實施例中，需要熱及/或壓力以將CTA溶解於水中。隨後在第VIII族貴金屬氫化催化劑(例如鉑、鈀、釕或銠催化劑)或替代類型之催化劑(例如鎳催化劑)存在下對其進行氫化。催化劑可為均相或非均相催化劑，且可以無載體形式提供或可負載於適合於此目的之任何類型材料上。載體材料一般為多孔材料，包括(但不限於)活性碳/木炭、氧化鋁、碳酸鈣、硫酸鋇、二氧化矽粉末、石英粉末或其組合。氫源通常為氫氣，但此亦可改變。在某些情況下，儘管氫化製程可在大氣壓力及環境溫度下發生，但在商業規模上通常施加熱及/或壓力。舉例而言，在某些實施例中，溫度為約200℃至約374℃，例如約250℃或250℃以上。壓力通常足以使CTA溶液維持液態形式(例如約50至約100atm)。實施CTA氫化所需氫之量通常超過還原所溶解雜質所需之量。舉例而言，氫化可在壓力容器、氫化器或塞式流動反應器內發生，或可藉由流動氫化實現，其中在氫氣存在下使所溶解CTA通過固定床催化劑。 A variety of hydrogenation conditions can be used in accordance with the present invention. CTA is typically dissolved in a solvent such as water. In some embodiments, heat and/or pressure is required to dissolve the CTA in water. This is subsequently hydrogenated in the presence of a Group VIII noble metal hydrogenation catalyst such as a platinum, palladium, rhodium or ruthenium catalyst or an alternative type of catalyst such as a nickel catalyst. The catalyst can be a homogeneous or heterogeneous catalyst and can be provided in a carrier free form or can be supported on any type of material suitable for this purpose. The support material is typically a porous material including, but not limited to, activated carbon/charcoal, alumina, calcium carbonate, barium sulfate, ceria powder, quartz powder, or combinations thereof. The hydrogen source is usually hydrogen, but this can also be changed. In some cases, although the hydrogenation process can occur at atmospheric pressure and ambient temperature, heat and/or pressure is typically applied on a commercial scale. For example, in certain embodiments, the temperature is from about 200 °C to about 374 °C, such as about 250 °C or above. The pressure is generally sufficient to maintain the CTA solution in a liquid form (e.g., from about 50 to about 100 atm). The amount of hydrogen required to effect hydrogenation of the CTA typically exceeds the amount required to reduce the dissolved impurities. For example, hydrogenation can occur in a pressure vessel, a hydrogenator or a plug flow reactor, or can be accomplished by flow hydrogenation wherein the dissolved CTA is passed through a fixed bed catalyst in the presence of hydrogen.

藉由一或多種物理程序回收經純化對苯二甲酸。舉例而言，一般經由自溶液(例如水)結晶產物來獲得PTA，因為大部分雜質(包括對甲苯甲酸、乙酸)及少量對苯二甲酸保留在溶液中。因此，使一些實施例中之混合物通過一或多個結晶器且進行減壓(其一般冷卻混合物且蒸發部分水，得到PTA晶體之漿液)。可藉由諸如過濾及/或離心之方式回收PTA，洗滌且乾燥，得到純所需材料。剩餘溶液稱為純工廠母液(PPML)。進行PTA與PPML之此分離的溫度可改變；然而，其通常約70℃至約160℃範圍內(例如約100℃或高於100℃)。 The purified terephthalic acid is recovered by one or more physical procedures. For example, PTA is typically obtained by crystallizing a product from a solution (eg, water) because most of the impurities (including Toluic acid, acetic acid) and a small amount of terephthalic acid remain in solution. Thus, the mixture in some embodiments is passed through one or more crystallizers and subjected to reduced pressure (which typically cools the mixture and evaporates a portion of the water to give a slurry of PTA crystals). The PTA can be recovered by filtration and/or centrifugation, washed and dried to give the pure desired material. The remaining solution is called pure factory mother liquor (PPML). The temperature at which this separation of PTA and PPML is carried out can vary; however, it typically ranges from about 70 °C to about 160 °C (e.g., about 100 °C or above 100 °C).

PPML一般包含水以及一定含量之對甲苯甲酸、乙酸及少量不純對苯二甲酸。PPML亦可包含苯甲酸及其他中間體及副產物。根據本發明，藉助於諸如圖1中所例示之方法純化PPML，其中類似識別符指類似組分或流體。儘管圖1中之示意性方法不欲限制本發明，但其可代表可採用如本申請案中所述之步驟及特徵的例示性系統。簡言之，在一些實施例中，使PPML與萃取劑接觸以便自其萃取芳族羧酸(例如對甲苯甲酸及苯甲酸)。萃取劑可採取多種形式且可自多種來源提供。萃取劑宜包含在液相蒸餾中所用之有機共沸添加劑，該液相係在對二甲苯氧化反應得到粗對苯二甲酸之後獲得。 PPML generally comprises water and a certain amount of p-toluic acid, acetic acid and a small amount of impure terephthalic acid. PPML may also contain benzoic acid and other intermediates and by-products. In accordance with the present invention, PPML is purified by means of a method such as that illustrated in Figure 1, wherein a similar identifier refers to a similar component or fluid. Although the illustrative method of FIG. 1 is not intended to limit the invention, it may represent an exemplary system that employs the steps and features described in this application. Briefly, in some embodiments, PPML is contacted with an extractant to extract an aromatic carboxylic acid (e.g., p-toluic acid and benzoic acid) therefrom. The extractant can take a variety of forms and can be provided from a variety of sources. The extractant preferably comprises an organic azeotrope additive for use in liquid phase distillation which is obtained after oxidation of p-xylene to give crude terephthalic acid.

首先參看圖1，「OR」表示諸如一般如上所述之對二甲苯之氧化反應。舉例而言，Ohkashi等人之美國專利第5,705,682號；及Parten之美國專利第6,143,926號及第6,150,553號中提供該等反應之其他論述，其各以引用的方式併入本文中。流體B表示在氧化反應期間形成之頂部冷凝物以及在氧化反應及移除固體粗對苯二甲酸之後所獲得的液相及氣相。因此，流體B主要包含水及乙酸(液體及/或蒸氣形式)。主要組分一般為乙酸(例如至少約50體積%)，且流體之剩餘部分一般為水，但少量(例如小於約5%、小於約2%)有機組分(例如乙酸甲酯)亦可存在於流體B中。使含液體及/或蒸氣之流體B與有機共沸添加劑在蒸餾塔30中接觸。共沸添加劑可改變，但宜為適用於共沸蒸餾乙酸與水之混合溶液的物質。舉例而言，在某些實施例中，共沸添加劑包含甲苯、二甲苯、乙苯、甲基丁基酮、氯苯、乙基戊醚、甲酸丁酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯、乙酸異丁酯、乙酸戊酯、乙酸甲酯、丙酸正丁酯、丙酸二異丁酯、丙醇、水或任何兩種或兩種以上此等或其他共沸添加劑之組合。塔30可為例如盤式塔或填充塔。舉例而言，Parten等人之美國專利第5,980,696號中提供使水與乙酸分離之共沸蒸餾製程的一般論述，該專利以引用的方式併入本文中。 Referring first to Figure 1, " OR " represents an oxidation reaction such as p-xylene generally as described above. Further discussion of such reactions is provided in U.S. Patent No. 5,705,682, the disclosure of which is incorporated herein by reference. Fluid B represents the top condensate formed during the oxidation reaction and the liquid and gas phases obtained after the oxidation reaction and removal of the solid crude terephthalic acid. Thus, fluid B primarily comprises water and acetic acid (in liquid and/or vapor form). The primary component is typically acetic acid (e.g., at least about 50% by volume), and the remainder of the fluid is typically water, although minor (e.g., less than about 5%, less than about 2%) organic components (e.g., methyl acetate) may also be present. In fluid B. The liquid B and/or vapor containing fluid B is contacted with the organic azeotrope in the distillation column 30 . The azeotropic additive may be changed, but is preferably a substance suitable for azeotropic distillation of a mixed solution of acetic acid and water. For example, in certain embodiments, the azeotrope additive comprises toluene, xylene, ethylbenzene, methyl butyl ketone, chlorobenzene, ethyl pentyl ether, butyl formate, n-propyl acetate, isopropyl acetate , n-butyl acetate, isobutyl acetate, amyl acetate, methyl acetate, n-butyl propionate, diisobutyl propionate, propanol, water or any two or more of these or other azeotropes A combination of additives. Tower 30 can be, for example, a tray column or a packed column. A general discussion of an azeotropic distillation process for separating water from acetic acid is provided in U.S. Patent No. 5,980,696, the entire disclosure of which is incorporated herein by reference.

在塔30內，使用有機共沸添加劑分離乙酸與水。可自塔底部移出含乙酸相，如流體G及J1。通常，流體G包含約95%乙酸及約5%水，且不含大量共沸添加劑。流體G經由再沸器60回收至塔30。離開塔30之熱乙酸流體J1通過熱交換器25，隨後返回氧化反應中。離開傾析器20之有機流體F1亦通過熱交換器25以便將來自乙酸流體J1之熱量傳送至有機流體F1，隨後有機流體F1以流體F2形式進入塔30。因此，有機流體F2在相對於離開傾析器20時之溫度提高的溫度下進入塔30。 Within column 30 , acetic acid and water are separated using an organic azeotrope additive. The acetic acid containing phase, such as fluids G and J1 , can be removed from the bottom of the column. Typically, fluid G contains about 95% acetic acid and about 5% water and does not contain significant amounts of azeotropic additives. The fluid G is recovered to the column 30 via the reboiler 60 . The hot acetic acid stream J1 leaving the column 30 passes through the heat exchanger 25 and is then returned to the oxidation reaction. The organic fluid F1 leaving decanter 20 also through a heat exchanger 25 to the heat from the fluid delivered to the organic acid J1 of fluid F1, then the organic fluid F1 F2 into column 30 in fluid form. Thus, the organic fluid F2 enters the column 30 at a temperature that increases relative to the temperature exiting the decanter 20 .

塔30內產生之氣相一般包含有機共沸添加劑以及水及乙酸甲酯。宜自塔30移除乙酸甲酯，因為在一些實施例中，其可能干擾塔30內之共沸分離。可自蒸餾塔以流體C形式移出氣相。可在冷凝器40內冷凝此流體，得到冷凝物流D。冷凝物流D一般包含有機共沸添加劑且可進一步包含水，可將水自混合物移除或可維持水作為冷凝物流D之組分。冷凝物流D之溫度可改變；然而，在例示性實施例中，流體D在約60℃與約100℃之間，諸如在約70℃與約90℃之間，在約75℃與約82℃之間(例如，在某些實施例中，約78℃或約80℃)。應注意冷凝物之溫度將隨冷凝物流D之組成(例如所用特定共沸添加劑)而略微改變。 The gas phase produced in column 30 generally comprises an organic azeotrope additive as well as water and methyl acetate. Methyl acetate is preferably removed from column 30 because, in some embodiments, it may interfere with azeotropic separation within column 30 . The gas phase can be removed from the distillation column in the form of fluid C. This fluid can be condensed in condenser 40 to provide condensate stream D. Condensate stream D generally comprises an organic azeotrope additive and may further comprise water, which may be removed from the mixture or may maintain water as a component of condensate stream D. The temperature of the condensate stream D can vary; however, in the exemplary embodiment, the fluid D is between about 60 ° C and about 100 ° C, such as between about 70 ° C and about 90 ° C, at about 75 ° C and about 82 ° C. Between (for example, in certain embodiments, about 78 ° C or about 80 ° C). It should be noted that the temperature of the condensate will vary slightly with the composition of the condensate stream D (e.g., the particular azeotrope additive used).

使PPML流A與流體D在混合器10中接觸。流體A與流體D之重量比可改變，且可視需要將其他組分添加至混合器(例如其他共沸添加劑或水)中。流體D與流體A之比率為約1：1至約5：1(例如約1.7：1至約2.1：1)。混合器10之性質可改變；其可包含萃取柱、靜態混合器、動態混合器(例如攪拌混合器)、泵或振盪器。 The PPML stream A is brought into contact with the fluid D in the mixer 10 . The weight ratio of fluid A to fluid D can vary, and other components can be added to the mixer (eg, other azeotrope additives or water) as desired. The ratio of fluid D to fluid A is from about 1:1 to about 5:1 (e.g., from about 1.7:1 to about 2.1:1). The nature of the mixer 10 can vary; it can include an extraction column, a static mixer, a dynamic mixer (such as a stirred mixer), a pump, or an oscillator.

流體A與流體D之所得混合物以混合流體E形式離開混合器10，且進入傾析器20中。傾析器可為可分離有機流體F1(例如富含有機共沸添加劑之流體F1)與水性流體K之任何組件。有時，可使用單個傾析器，其可降低系統之資金成本且降低共沸添加劑之水解程度。此外，將原先存在於PPML流A中之某些有機雜質(例如對甲苯甲酸、苯甲酸等)萃取至有機相中，且因此經由有機流體F1移除。將乙酸甲酯(原先存在於來自蒸餾塔30之流體C中)分配於水性流體K1中。 The resulting mixture of fluid A and fluid D exits mixer 10 in the form of mixed fluid E and enters decanter 20 . Decanter organic fluid F1 may be detachable (e.g. azeotropic rich fluid F1 or the additive) with any component of the aqueous fluid K. Sometimes a single decanter can be used which reduces the capital cost of the system and reduces the degree of hydrolysis of the azeotrope additive. In addition, certain organic impurities (eg, p-toluic acid, benzoic acid, etc.) originally present in the PPML stream A are extracted into the organic phase and thus removed via the organic fluid F1 . Methyl acetate (previously present in fluid C from distillation column 30 ) is dispensed into aqueous fluid K1 .

將有機流體F2遞送至蒸餾塔30。儘管圖式顯示流體F2之入口在蒸餾塔之中部，但此並不欲具有限制性；流體F2可在蒸餾塔之頂部、中部或底部或在其間的任何階段進入塔。隨著某些有機組分經由流體F2進入，應注意可能影響離開蒸餾塔30之流體C及J1之組成。一般而言，經由流體F2進入蒸餾塔之有機組分中之大部分保留在乙酸相中，且經由流體J1自塔30移除。 The organic fluid F2 is delivered to the distillation column 30 . Although the figure shows that the inlet of fluid F2 is in the middle of the distillation column, this is not intended to be limiting; fluid F2 can enter the column at the top, middle or bottom of the distillation column or at any stage therebetween. As certain organic components enter via fluid F2 , care should be taken to affect the composition of fluids C and J1 leaving distillation column 30 . In general, most of the organic components entering the distillation column via fluid F2 remain in the acetic acid phase and are removed from column 30 via fluid J1 .

水性流體K1可經處理以使水可再用於該方法中(例如在CTA純化中)、出於其他目的進行回收或以廢水形式丟棄。如圖1中所示，離開回收塔70之經加熱流出水L1可通過熱交換器65，其與離開傾析器20之水性流體K1呈熱交換關係。因此可在顯著提高之溫度下將離開熱交換器65之水性流體K2傳遞至塔70。流體K2之溫度可改變，以使得流體K2可包含水性液相及/或氣相。在提高之溫度下提供流體K2之益處在於可顯著減少必須引入至塔70中(經由流體M)以有效汽提有機組分之蒸汽的量。在某些實施例中，可藉由使水相K2通過回收塔70而自PPML萃取之水相汽提可能存在於水性流體K2中之非所需乙酸甲酯，該回收塔70係經設計以汽提出任何殘餘有機物質。應注意，少量有機相(例如包含有機共沸添加劑之有機相)亦可存在於流體K2中，且在一些實施例中，亦可藉助於回收塔70移除該殘餘有機物質。一般而言，經由使水相流體K2與經顯示為進入塔70之流體M的蒸汽接觸來實現自水相汽提有機物質。或者，可使用塔70上之再沸器來替代流體M。為有效汽提有機組分，一般應將待處理之流體加熱至約40℃至約140℃(包括60℃至100℃)，例如約95℃。潔淨水可經由流體L2例如在塔之底部離開塔。回收塔70可進一步配備有冷凝器50，其將回流以及蒸氣排放及液體產物返至塔之頂部。 The aqueous fluid K1 can be treated to allow the water to be reused in the process (e.g., in CTA purification), recovered for other purposes, or disposed of in the form of wastewater. As shown in FIG. 1, the heated effluent water L1 exiting the recovery column 70 can pass through a heat exchanger 65 in heat exchange relationship with the aqueous fluid K1 exiting the decanter 20 . The aqueous fluid K2 leaving the heat exchanger 65 can thus be transferred to the column 70 at a significantly elevated temperature. The temperature of the fluid K2 can be varied such that the fluid K2 can comprise an aqueous liquid phase and/or a gas phase. The benefit of providing fluid K2 at elevated temperatures is that the amount of steam that must be introduced into column 70 (via fluid M ) to effectively strip the organic components can be significantly reduced. In certain embodiments, the aqueous phase may be by K2 by recovery column 70 was extracted from the aqueous phase stripper PPML may be present in the aqueous fluid of undesired K2, methyl acetate recovery column 70 the system is designed to Steam out any residual organic matter. It should be noted that a small amount of organic phase (e.g., an organic phase comprising an organic azeotrope additive) may also be present in fluid K2 , and in some embodiments, the residual organic material may also be removed by means of recovery column 70 . In general, stripping of the organic material from the aqueous phase is achieved by contacting the aqueous phase fluid K2 with the vapor shown as fluid M entering the column 70 . Alternatively, a reboiler on column 70 can be used in place of fluid M. To effectively strip the organic component, the fluid to be treated is typically heated to a temperature of from about 40 ° C to about 140 ° C (including 60 ° C to 100 ° C), such as about 95 ° C. The clean water can exit the column via fluid L2, for example at the bottom of the column. The recovery column 70 can be further equipped with a condenser 50 that returns reflux and vapor effluent and liquid products to the top of the column.

流體L2含有雜質(例如羧酸、金屬)，該等雜質使得流體L2不適用於PTA工廠之其他部分。此外，由於PPMLSX製程之操作溫度及在此等溫度下乙酸的不良排除，可能發生逆滲透膜之積垢及結垢。出人意料地，已發現對流體L2進行預處理繼而逆滲透可產生適用於PTA工廠之其他部分的去礦物質水流。特定言之，用鹼溶液及超濾預處理L2使得逆滲透成為獲得去礦物質水之經濟且有效方法。在離開PPMLSX製程後，在小於7(包括2-7、4、5、6及7)之pH下的水性溶離流體L2具有表1中之以下組成： Fluid L2 contains impurities (e.g., carboxylic acid, metal) that make fluid L2 unsuitable for use in other parts of the PTA plant. In addition, fouling and fouling of the reverse osmosis membrane may occur due to the operating temperature of the PMLLSX process and the poor elimination of acetic acid at such temperatures. Surprisingly, it has been found that pretreatment of fluid L2 followed by reverse osmosis produces a demineralized water stream suitable for use in other parts of the PTA plant. In particular, pretreatment of L2 with an alkaline solution and ultrafiltration makes reverse osmosis an economical and effective method for obtaining demineralized water. After leaving the PMLLSX process, the aqueous dissolving fluid L2 at a pH of less than 7 (including 2-7, 4, 5, 6 and 7) has the following composition in Table 1:

在逆滲透製程中使用L2之前，處理L2以移除羧酸及溶解之金屬，且調節pH。此時，L2進入中和器100，在此處水性流體與鹼(例如氫氧化鈉、氫氧化鉀、氫氧化鈣、碳酸鈉、碳酸鉀、碳酸鈣及其混合物)接觸以提高pH至8-10之間，包括9。水性流體中鹼之濃度可在5wt.%至90wt.%範圍內，包括5wt.%至80wt.%、10wt.%至80wt.%、10wt.%至90wt.%、20wt.%至90wt.%、20wt.%至80wt.%、20wt.%至70wt.%、30wt.%至90wt.%、30wt.%至80wt.%、30wt.%至70wt.%及30wt.%至60wt.%。濃度需要足以達到500至2000ppm之鹼濃度。另外，將溶解及懸浮之羧酸(例如乙酸、對苯二甲酸、CBA、對甲苯甲酸、苯甲酸)轉化成其各別可溶性鹽。舉例而言，若使用氫氧化鈉作為鹼，則將乙酸轉化成乙酸鈉。另外，將溶解之金屬(例如鈷、錳)轉化成金屬氫氧化物，且沈澱於水性流體中。中和器100可為使得流體L2與鹼之間充分接觸之任何器件。舉例而言，可使用逆流洗滌器、重力饋料傾析器(例如其中L2垂直通過鹼溶液)、靜態混合器、噴淋器。以下為當使用氫氧化鈉作為鹼溶液時pH調節流體N之組成： Before use in reverse osmosis processes in L2, L2 processed to remove and dissolve the metal carboxylate, and adjust the pH. At this point, L2 enters neutralizer 100 where the aqueous fluid is contacted with a base such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, and mixtures thereof to increase the pH to 8- Between 10, including 9. The concentration of the base in the aqueous fluid may range from 5 wt.% to 90 wt.%, including 5 wt.% to 80 wt.%, 10 wt.% to 80 wt.%, 10 wt.% to 90 wt.%, 20 wt.% to 90 wt.%. 20 wt.% to 80 wt.%, 20 wt.% to 70 wt.%, 30 wt.% to 90 wt.%, 30 wt.% to 80 wt.%, 30 wt.% to 70 wt.%, and 30 wt.% to 60 wt.%. The concentration needs to be sufficient to achieve an alkali concentration of 500 to 2000 ppm. In addition, the dissolved and suspended carboxylic acid (e.g., acetic acid, terephthalic acid, CBA, p-toluic acid, benzoic acid) is converted to its respective soluble salt. For example, if sodium hydroxide is used as the base, acetic acid is converted to sodium acetate. In addition, the dissolved metal (e.g., cobalt, manganese) is converted to a metal hydroxide and precipitated in an aqueous fluid. Neutralizer 100 can be any device that provides sufficient contact between fluid L2 and the base. For example, a counter current scrubber, a gravity feed decanter (eg, where L2 is passed vertically through an alkaline solution), a static mixer, a shower can be used. The following is the composition of the pH adjusting fluid N when sodium hydroxide is used as the alkaline solution:

隨後，將pH調節流體N傳送至超濾單元120，或在單元120前視情況存在之儲料槽110，以移除懸浮固體。此處，使pH調節流體N與至少一種超濾膜接觸以移除金屬氫氧化物，形成經處理流體P。舉例而言，具有約0.1微米之孔徑的超濾膜KMS HFMTM-180對於氫氧化鈷及氫氧化錳具有>99.5%之排除效能，從而在經處理流體中留下殘餘<0.05ppm之鈷及錳。以下為當使用氫氧化鈉作為鹼溶液時經處理流體P之組成： Subsequently, the pH adjusting fluid N is transferred to the ultrafiltration unit 120 , or the sump 110 is present in the front of the unit 120 to remove suspended solids. Here, the pH adjusting fluid N is contacted with at least one ultrafiltration membrane to remove the metal hydroxide to form a treated fluid P. For example, an ultrafiltration membrane KMS HFMTM-180 having a pore size of about 0.1 micron has an exclusion efficiency of >99.5% for cobalt hydroxide and manganese hydroxide, leaving a residual <0.05 ppm of cobalt and manganese in the treated fluid. . The following is the composition of the treated fluid P when sodium hydroxide is used as the alkaline solution:

接著使經處理流體P進入逆滲透單元130中，在其中移除鈉、乙酸鹽及其他離子性物質且使pH降低至約6-8之間，從而產生去礦物質水流Q1及Q。視情況，可一起採用第二逆滲透單元140與單元130以進一步降低鈉、乙酸鹽及其他離子性物質之濃度。此處，將第一通滲透物R1饋入單元140中，且抽去去礦物質流體Q2。此外，單元130及140可以環型組態使用，其中將單元140滲透物R2之一部分回收返回單元130。舉例而言，經處理流體P可通過兩個可串聯排列逆滲透KMS Fluid Systems TFC-SW膜，從而產生去礦物質水流Q，其具有0.97ppm鈉及2.49ppm乙酸鹽，且pH為6。此外，本發明不限於一個或兩個逆滲透單元。視應用、工廠規模及位置而定，可以串聯或以環型組態與裝置130及140一起採用其他單元。以下為當使用氫氧化鈉作為鹼溶液時去礦物質水流Q之組成： The treated fluid P is then passed to a reverse osmosis unit 130 where sodium, acetate and other ionic species are removed and the pH is lowered to between about 6-8 to produce demineralized water streams Q1 and Q. The second reverse osmosis unit 140 and unit 130 may be employed together to further reduce the concentration of sodium, acetate, and other ionic species, as appropriate. Here, the first pass permeate R1 is fed into the unit 140 and the demineralized fluid Q2 is withdrawn . Additionally, units 130 and 140 can be used in a ring configuration where a portion of unit 140 permeate R2 is recycled back to unit 130 . For example, the treated fluid P can be passed through two reverse osmosis KMS Fluid Systems TFC-SW membranes in series to produce a demineralized water stream Q having 0.97 ppm sodium and 2.49 ppm acetate and a pH of 6. Furthermore, the invention is not limited to one or two reverse osmosis units. Depending on the application, plant size and location, other units may be employed in series or in a ring configuration with devices 130 and 140 . The following is the composition of the demineralized water stream Q when using sodium hydroxide as the alkaline solution:

如表4中所示，去礦物質水流Q實質上不含金屬化合物、Mn、K、Ca、Mg、Fe及Co(亦即鹼金屬鈉除外，總金屬濃度在0.01ppm與1ppm之間，包括在0.01ppm與0.1ppm之間及在0.01ppm與0.05ppm之間)，同時亦具有較低鈉及乙酸鹽濃度。 As shown in Table 4, the demineralized water stream Q is substantially free of metal compounds, Mn, K, Ca, Mg, Fe, and Co (i.e., alkali metal sodium, the total metal concentration is between 0.01 ppm and 1 ppm, including Between 0.01 ppm and 0.1 ppm and between 0.01 ppm and 0.05 ppm) also has lower sodium and acetate concentrations.

去礦物質水流Q可用於PTA工廠中之其他製程。該等製程包括：粗對苯二甲酸結晶、結晶水洗滌、對苯二甲酸純化、溶劑回收、蒸餾、分離及蒸汽產生。另外，可將去礦物質水流引入標準廢水處理流體中以在廢水處理工廠中進行下游加工。 The demineralized water stream Q can be used in other processes in the PTA plant. Such processes include: crude terephthalic acid crystallization, crystallization water washing, terephthalic acid purification, solvent recovery, distillation, separation, and steam generation. Additionally, demineralized water streams can be introduced into standard wastewater treatment fluids for downstream processing in wastewater treatment plants.

10‧‧‧混合器 10‧‧‧ Mixer

20‧‧‧傾析器 20‧‧‧ Decanter

25‧‧‧熱交換器 25‧‧‧ heat exchanger

30‧‧‧蒸餾塔/塔 30‧‧‧Distillation tower/tower

40‧‧‧冷凝器 40‧‧‧Condenser

50‧‧‧冷凝器 50‧‧‧Condenser

60‧‧‧再沸器 60‧‧‧ reboiler

65‧‧‧熱交換器 65‧‧‧ heat exchanger

70‧‧‧回收塔/塔 70‧‧‧Recycling tower/tower

A‧‧‧PPML流/流體 A‧‧‧PPML flow/fluid

B‧‧‧流體 B‧‧‧ fluid

C‧‧‧流體 C‧‧‧ fluid

D‧‧‧冷凝物流/流體 D‧‧‧ Condensate / Fluid

E‧‧‧混合流體 E‧‧‧ mixed fluid

F1‧‧‧有機流體 F1‧‧‧Organic fluid

F2‧‧‧有機流體/流體 F2‧‧‧Organic fluids/fluids

G‧‧‧流體 G‧‧‧ fluid

J1‧‧‧流體/熱乙酸流體 J1‧‧‧ Fluid/Hot Acetic Acid Fluid

K1‧‧‧水性流體 K1‧‧‧aqueous fluid

K2‧‧‧水性流體/水相流體 K2‧‧‧aqueous fluid/aqueous fluid

L1‧‧‧流出水 L1‧‧‧ outflow water

L2‧‧‧流體 L2‧‧‧ fluid

M‧‧‧流體 M‧‧‧ fluid

Claims

一種處理由純工廠母液溶劑萃取製程產生之水性溶離流體的方法，其包含：a.藉由使該水性流體與鹼接觸來提高該水性流體之pH以形成pH調節流體；b.使該pH調節流體與過濾器接觸以形成經處理流體；及c.使該經處理流體與逆滲透單元接觸以形成去礦物質水流。 A method of treating an aqueous dissolved fluid produced by a pure plant mother liquor solvent extraction process, comprising: a. increasing the pH of the aqueous fluid to form a pH adjusting fluid by contacting the aqueous fluid with a base; b. adjusting the pH Fluid contacts the filter to form a treated fluid; and c. contacts the treated fluid with a reverse osmosis unit to form a demineralized water stream.

如請求項1之方法，其中該過濾器為超濾膜。 The method of claim 1, wherein the filter is an ultrafiltration membrane.

如請求項2之方法，其中該超濾膜具有0.01微米至0.1微米之平均孔徑。 The method of claim 2, wherein the ultrafiltration membrane has an average pore diameter of from 0.01 micrometers to 0.1 micrometers.

如請求項1之方法，其中該pH調節流體之pH係在8-12之間。 The method of claim 1, wherein the pH adjusting fluid has a pH between 8 and 12.

如請求項1之方法，其中該鹼係選自由氫氧化鈉、氫氧化鉀及其混合物組成之群。 The method of claim 1, wherein the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, and mixtures thereof.

如請求項5之方法，其中該鹼為氫氧化鈉。 The method of claim 5, wherein the base is sodium hydroxide.

如請求項6之方法，其中鈉金屬之濃度係在500與2000ppm之間。 The method of claim 6 wherein the concentration of sodium metal is between 500 and 2000 ppm.

如請求項1之方法，其中該水性流體之pH係在3-5之間。 The method of claim 1, wherein the aqueous fluid has a pH between 3-5.

如請求項1之方法，其中該經處理流體含有金屬化合物，其總金屬濃度在0.01ppm與1ppm之間。 The method of claim 1, wherein the treated fluid contains a metal compound having a total metal concentration between 0.01 ppm and 1 ppm.

如請求項9之方法，其中該總金屬濃度係在0.01ppm與0.1ppm之間。 The method of claim 9, wherein the total metal concentration is between 0.01 ppm and 0.1 ppm.

一種使用獲自純工廠母液溶劑萃取製程之去礦物質水流的方法，其包含：a.藉由使由該純工廠母液溶劑萃取製程產生之水性流體與鹼接觸提高該水性流體的pH來形成pH調節流體； b.使該pH調節流體與過濾器接觸以形成經處理流體；c.使該經處理流體與逆滲透單元接觸以形成去礦物質水流；及d.輸送該去礦物質水流至PTA工廠中之其他製程。 A method of using a demineralized water stream obtained from a pure plant mother liquor solvent extraction process, comprising: a. forming a pH by contacting an aqueous fluid produced by the pure plant mother liquor solvent extraction process with a base to increase the pH of the aqueous fluid Regulating fluid; b. contacting the pH adjusting fluid with a filter to form a treated fluid; c. contacting the treated fluid with a reverse osmosis unit to form a demineralized water stream; and d. delivering the demineralized water stream to a PTA plant Other processes.

如請求項11之方法，其中該過濾器為超濾膜。 The method of claim 11, wherein the filter is an ultrafiltration membrane.

如請求項12之方法，其中該超濾膜具有0.01微米至0.1微米之平均孔徑。 The method of claim 12, wherein the ultrafiltration membrane has an average pore diameter of from 0.01 micrometers to 0.1 micrometers.

如請求項11之方法，其中該pH調節流體之pH係在8-10之間。 The method of claim 11, wherein the pH adjusting fluid has a pH between 8 and 10.

如請求項11之方法，其中該鹼係選自由氫氧化鈉、氫氧化鉀及其混合物組成之群。 The method of claim 11, wherein the base is selected from the group consisting of sodium hydroxide, potassium hydroxide, and mixtures thereof.

如請求項15之方法，其中該鹼為氫氧化鈉。 The method of claim 15, wherein the base is sodium hydroxide.

如請求項16之方法，其中鈉金屬之濃度係在500與2000ppm之間。 The method of claim 16, wherein the concentration of sodium metal is between 500 and 2000 ppm.

如請求項11之方法，其中該水性流體之pH係在3-5之間。 The method of claim 11, wherein the aqueous fluid has a pH between 3-5.

如請求項11之方法，其中該經處理流體含有金屬化合物，其總金屬濃度在0.01ppm與1ppm之間。 The method of claim 11, wherein the treated fluid contains a metal compound having a total metal concentration between 0.01 ppm and 1 ppm.

如請求項19之方法，其中該總金屬濃度係在0.01ppm與0.1ppm之間。 The method of claim 19, wherein the total metal concentration is between 0.01 ppm and 0.1 ppm.

一種在由純工廠母液溶劑萃取製程產生之水性溶離流體中將有機酸轉化成酸鹽之方法，其包含：使該水性溶離流體與鹼接觸，其中該水性溶離流體在與該鹼接觸前具有600ppm至5000ppm之有機酸濃度。 A method of converting an organic acid to an acid salt in an aqueous dissolved fluid produced by a pure plant mother liquor solvent extraction process, comprising: contacting the aqueous dissolved fluid with a base, wherein the aqueous dissolved fluid has 600 ppm prior to contact with the base Organic acid concentration to 5000 ppm.

如請求項21之方法，其中該有機酸濃度係在1000ppm至5000ppm之間。 The method of claim 21, wherein the organic acid concentration is between 1000 ppm and 5000 ppm.

如請求項22之方法，其中該有機酸濃度係在2000ppm至5000ppm之間。 The method of claim 22, wherein the organic acid concentration is between 2000 ppm and 5000 ppm.

如請求項21之方法，其中該有機酸濃度係在1000ppm至3000 ppm之間。 The method of claim 21, wherein the organic acid concentration is between 1000 ppm and 3000 Between ppm.

如請求項21至24中任一項之方法，其中該有機酸係選自由以下各者組成之群：乙酸、對苯二甲酸、對甲苯甲酸、苯甲酸及其混合物。 The method of any one of claims 21 to 24, wherein the organic acid is selected from the group consisting of acetic acid, terephthalic acid, p-toluic acid, benzoic acid, and mixtures thereof.

一種自pH為至少8之水性流體移除氫氧化鈷及氫氧化錳的方法，其包含：使該水性流體與過濾器接觸，其中該水性流體在與該過濾器接觸前具有500ppm至2000ppm之鈉濃度。 A method of removing cobalt hydroxide and manganese hydroxide from an aqueous fluid having a pH of at least 8, comprising: contacting the aqueous fluid with a filter, wherein the aqueous fluid has a sodium content of from 500 ppm to 2000 ppm prior to contact with the filter concentration.

如請求項26之方法，其中該水性流體之pH為8-10。 The method of claim 26, wherein the aqueous fluid has a pH of from 8 to 10.

如請求項26之方法，其中該過濾器包含超濾膜。 The method of claim 26, wherein the filter comprises an ultrafiltration membrane.

一種自pH為至少8之水性流體移除鈉鹽之方法，其包含：使該水性流體與逆滲透單元接觸，其中該水性流體在與該逆滲透單元接觸前具有小於0.1ppm之鈷濃度及500ppm至3000ppm之乙酸鹽濃度。 A method of removing a sodium salt from an aqueous fluid having a pH of at least 8 comprising: contacting the aqueous fluid with a reverse osmosis unit, wherein the aqueous fluid has a cobalt concentration of less than 0.1 ppm and 500 ppm prior to contact with the reverse osmosis unit The acetate concentration to 3000 ppm.

如請求項29之方法，其中該水性流體之pH為8-10。 The method of claim 29, wherein the aqueous fluid has a pH of from 8 to 10.

如請求項29之方法，其中在與該逆滲透單元接觸前，該乙酸鹽濃度為1000ppm至3000ppm。 The method of claim 29, wherein the acetate concentration is from 1000 ppm to 3000 ppm prior to contact with the reverse osmosis unit.

一種純工廠母液溶劑萃取水性溶離流體，其包含：a.濃度為600ppm至3000ppm之乙酸；b.濃度為50ppm至450ppm之對苯二甲酸；及c.濃度為0.1ppm至50ppm之金屬，其中該水性溶離流體之pH為小於5。 A pure plant mother liquor solvent extraction aqueous dissolving fluid comprising: a. acetic acid having a concentration of 600 ppm to 3000 ppm; b. terephthalic acid having a concentration of 50 ppm to 450 ppm; and c. a metal having a concentration of 0.1 ppm to 50 ppm, wherein The pH of the aqueous dissolving fluid is less than 5.

如請求項32之水性溶離流體，其進一步包含：d.濃度為0至20ppm之羧基苯甲醛；e.10至620ppm之對甲苯甲酸；及f.20至350ppm之苯甲酸。 The aqueous dispersion fluid of claim 32, which further comprises: d. carboxybenzaldehyde having a concentration of 0 to 20 ppm; p-toluic acid of e. 10 to 620 ppm; and benzoic acid of f. 20 to 350 ppm.

一種水性流體組合物，其包含： a.鈉濃度為500ppm至2000ppm之鈉鹽；及b.金屬濃度為0.05ppm至約50ppm之金屬氫氧化物，其中該水性流體之pH為至少8。 An aqueous fluid composition comprising: a sodium salt having a sodium concentration of from 500 ppm to 2000 ppm; and b. a metal hydroxide having a metal concentration of from 0.05 ppm to about 50 ppm, wherein the pH of the aqueous fluid is at least 8.

如請求項34之水性流體組合物，其中該金屬氫氧化物之金屬離子係選自由鈷、錳及其混合物組成之群。 The aqueous fluid composition of claim 34, wherein the metal ion of the metal hydroxide is selected from the group consisting of cobalt, manganese, and mixtures thereof.

如請求項34或35之水性流體組合物，其進一步包含：c.濃度為0至20ppm之羧基苯甲醛；d.酸濃度為50至450ppm之對苯二甲酸鹽；e.酸濃度為10至620ppm之對甲苯甲酸鹽；及f.酸濃度為20至350ppm之苯甲酸鹽。 The aqueous fluid composition of claim 34 or 35, further comprising: c. carboxybenzaldehyde having a concentration of 0 to 20 ppm; d. a terephthalate having an acid concentration of 50 to 450 ppm; and an acid concentration of 10 To 620 ppm of p-toluate; and f. acidity of 20 to 350 ppm of benzoate.

一種水性流體組合物，其包含：a.0.01至0.1ppm之鈷；及b.0.01至0.1ppm之錳，其中該水性流體之pH為至少8。 An aqueous fluid composition comprising: a. 0.01 to 0.1 ppm of cobalt; and b. 0.01 to 0.1 ppm of manganese, wherein the aqueous fluid has a pH of at least 8.

如請求項37之水性流體組合物，其進一步包含：c.酸濃度為50至450ppm之對苯二甲酸鹽；d.濃度為0至20ppm之羧基苯甲醛；e.酸濃度為10至620ppm之對甲苯甲酸鹽；及f.酸濃度為20至350ppm之苯甲酸鹽。 The aqueous fluid composition of claim 37, further comprising: c. a terephthalate having an acid concentration of 50 to 450 ppm; d. a carboxybenzaldehyde having a concentration of 0 to 20 ppm; and an acid concentration of 10 to 620 ppm P-toluate; and f. benzoate having an acid concentration of 20 to 350 ppm.

如請求項37或38之水性流體，其進一步包含濃度為500至2000ppm之鈉。 The aqueous fluid of claim 37 or 38, which further comprises sodium at a concentration of from 500 to 2000 ppm.

一種潔淨水流組合物，其包含：a.濃度為0.5ppm至20ppm之乙酸鹽；及b.濃度為0.1ppm至10ppm之鈉，其中該水流具有6至8之pH且實質上不含金屬。 A clean water stream composition comprising: a. an acetate having a concentration of from 0.5 ppm to 20 ppm; and b. a sodium having a concentration of from 0.1 ppm to 10 ppm, wherein the water stream has a pH of from 6 to 8 and is substantially free of metal.

如請求項40之潔淨水流組合物，其中該等金屬係選自由K、Mg、Ca、Co、Fe、Mn及其混合物組成之群。 The clean water stream composition of claim 40, wherein the metal is selected from the group consisting of K, Mg, Ca, Co, Fe, Mn, and mixtures thereof.

如請求項40之潔淨水流組合物，其中金屬之濃度為0.01ppm至1ppm。 A clean water stream composition according to claim 40, wherein the concentration of the metal is from 0.01 ppm to 1 ppm.

如請求項40之潔淨水流組合物，其中該等金屬為Mg及Co，且該等金屬之濃度為0.01ppm至0.05ppm。 The clean water stream composition of claim 40, wherein the metals are Mg and Co, and the concentration of the metals is from 0.01 ppm to 0.05 ppm.