CN1115317C - 连续生产二羟基二芳基烷烃的方法 - Google Patents
连续生产二羟基二芳基烷烃的方法 Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种通过新鲜酚、来自副产物分解的酚及异亚烷基酚与酮的反应连续生产二羟基二芳基烷烃(双酚)的方法。此方法通过结晶过程从反应混合物中回收大部分双酚,所得母液经蒸馏与酚分离。酚返回反应中,蒸馏所得釜残,在添加碱性催化剂后,以反应性精馏分解。经塔顶出来的酚及异亚烷基酚返回反应;从第一反应塔出来的釜残,经酸化及在第二反应性精馏中于酸催化剂存在下进一步被分解为精馏的酚,再返回反应,而釜残则被处置。
Description
本发明涉及一种通过新鲜酚、由副产物分解的酚及异亚烷基酚与酮的反应连续地生产二羟基二芳基烷烃(双酚类)的方法。这种方法,通过结晶回收反应混合物中大部分的双酚,并通过蒸馏分离所得母液与酚。再将酚返回反应,而蒸馏所得釜残,经添加一种碱催化剂后,通过反应精馏加以分解。顶部产出的酚及异亚烷基酚再返回用于反应;将第一反应塔釜残加以酸化,并在第二反应精馏中于酸催化剂存在下进一步分解为酚及釜残,酚经蒸馏再循环用于反应,而釜残即排出。
酮与酚经酸催化反应产生双酚是已知的。在这方面有许多不同的建议(参见如US-A2775620,EP-A342758,EP-A616993,DE-OS3833900,US-A4308404,US-A4308405,EP-A630878,US-A4876391,US-A3242219)。
在乌尔曼工业化学百科全书第五版第A19卷,348-352页,有关于双酚生产的较老文献的综述。通常,双酚,尤其是双酚A(BPA),是工业上最重要的双酚类,采用将酮及酚加至由处理双酚所得循环母液中的方法制备,将这种混合物通过酸性离子交换剂并进行转化成双酚的反应。还可回收反应混合物中未反应的酮,并将其返回反应。该反应混合物经冷却,如若需要,可使双酚作为酚加成物而结晶出来,并加以分离和用酚洗涤。采用闪蒸方法将酚从加成物中分离出来,并回收纯双酚。使来自结晶过程的母液穿过酸性离子交换剂,将其中所含异构物进行重排,以形成双酚。由此形成的双酚经结晶分离,将所得结晶再通过第一结晶步骤。将一部分现在所得的母液(约10-20%)搁置一旁,大部分返回反应。从搁置一旁的部分母液中蒸馏出酚,再将其返回反应。排放蒸馏过程所得残渣,并用于制备例如酚树脂。
在这种较为复杂的方法中,母液反复穿过催化剂。在此过程中形成了许多异构物及副产物,以及一些必须小心地通过进一步结晶从双酚中加以分离出的带色化合物。再则,在搁置一旁并最终被排出部分中,还会损失相当数量的有价值的化合物,诸如双酚及异构物。由母液中的这种分离肯定是重要的,而不致使无用和有干扰作用的化合物变得太多。
因此,曾对被排放部分进行过处理及分解的研究,以图回收这些对用于生产双酚有价值的原料。为此,还有许多不同的建议。在约300℃下热解有可能得到适中收率的酚及亚烷基酚,但它们仍需充分提纯(US-A2497503)。加氢处理也可得到有价值的产物,如EP-A17852所述。也可用酸碱化合物加速这种分解。但是,用酸,诸如用硫酸或苯磺酸(US-A3466337),得到的只是酚。另一方面,碱性催化剂也可分解该排放物料为酚及异亚烷基酚。所述催化剂为碱金属化合物,诸如NaOH、KOH、NaHCO3、醋酸钠、次磷酸钠、K2CO3、MgO及异丙醇铝,(US-A4277628、US-A4594459、US-A4131749)。此种方法虽可使该部分排放物分解,但操作为间歇或半连续。完全的连续工艺尚未见报道。
至于对纯度较高的双酚,这些方法均已有所改进,即在分离第一部分双酚之后,将来自分解的酚/异亚烷基酚混合物加至第一母液中。此混合物再通过酸催化剂,使异亚烷基酚与酚的反应过程和重排过程同时进行。再用结晶方法从混合物中分离出第二部分双酚和使第二母液用于分解。将第二部分双酚加至第一结晶过程中。由此尽管双酚纯度会有一些提高,但由于有附加循环(见US-A4954661),这种方法变得更为复杂。
也曾提出,对在上述双酚工艺中的第二母液,或在分离第一部分双酚之后及重排之后的第一母液,应当至少通过蒸馏加以部分处理,以便更好利用其中所含有价值的产物。再将由此得到的双酚重新加至第一结晶步骤中加以提纯。将含异构物的低沸组分送去反应(WO9420445,EP-A552518)。但其困难在于,难以合理的费用,从大大富集了异构物及副产物的母液中,获得含极少量并难分离的苯并二氢吡喃及1,2-二氢化茚的高纯馏份,而又不致过度增多无用残渣和降低收率。正因为如此,也只得废弃一部分的蒸馏产物。
蒸馏所得含少量双酚的馏份也可加以分解,分解产物再返回工艺过程中(EP-A332203)。
现已发现,若用酮及用由分解所得的异亚烷基酚与酚反应,采用简单全连续的工艺,通过下述方式可得到最好的高纯双酚收率:尽可能地少量生成异构物及副产物,蒸馏出反应混合物中未反应的酮,还可分离出酸性组分,用结晶方法分离大部分其中所含的双酚,合并来自结晶步骤的母液和洗涤酚,蒸馏出酚并将其加至反应中,混合釜残与碱催化剂,并在第一反应精馏中将其分解为顶部馏出的且二者均进入反应的酚及异亚烷基酚,酸化反应精馏中所得的釜残,并在酸性催化剂存在下在第二反应精馏中将其分解成为酚,酚再加至反应中,而残渣随即排出。
按照本发明方法适宜的芳基羟基化合物在对位上是未被取代的,并不含二级取代基团,如氰基团、羧基团或硝基团;可述及的实例有酚、o-及m-甲酚、2,6-二甲酚、o-叔丁基酚、2-甲基6-叔丁基酚、o-环己酚、o-苯基苯酚、o-异丙基酚、2-甲基-6-环戊基酚、o-及m-氯酚、2,3,6-三甲酚。优选化合物为酚、o-及m-甲酚,2,6-二甲酚、o-叔丁基酚及o-苯基苯酚;酚是特别优选的。
适宜的酮在羰基官能上包括至少一个脂肪基团;可述及的实例是丙酮、甲乙酮、甲基丙基酮、甲基异丙基酮、乙酮、苯乙酮、环己酮、环戊酮、甲基-、二甲基-、及三甲基-环己酮,它们也可具有成对的甲基基团,诸如3,3-二甲基-5-甲基环己酮(氢化异佛尔酮)。优选化合物为丙酮、苯乙酮、环己酮及其含甲基基团的同系物;丙酮是特别优选的。
用于碱分解的适宜催化剂是文献中描述的那些,优选为碱金属氧化物和氢氧化物,特别优选的是NaOH及KOH。按照本发明的方法,将它们加至分解离析物的熔融物中,并加以溶解和均匀分布,温度最方便是在100至200℃之间,优选在120至180℃。
用于酸分解的适宜催化剂是文献中所描述的那些,优选为硫酸、磷酸、亚磷酸,及其部分盐,诸如NH4HSO3、NaHSO4、KHSO4、NaH2PO4、KH2PO4、NH4H2PO4、NH4H2PO3、KH2PO3及同系物,也可以是这些酸的有机衍生物,即芳烃磺酸及二磺酸,诸如苯磺酸、甲苯磺酸、二甲苯磺酸、酚基磺酸、二苯基二磺酸、二苯基醚二磺酸、而后是芳烃磷酸及膦酸,诸如苯-、甲苯-、二甲苯-磷酸和-膦酸、二苯基二磷酸及二苯基二膦酸,也可以是固体酸,诸如酸式氧化铝类、氧化铝类,如膨润土、蒙脱土、沸石、氧化钛、氧化锆、氧化铌、氧化钽;酸性氧化铝类是优选的。
加至待分解混合物中的催化剂数量为0.01至5%(重量),优选在0.05至3%(重量),特别优选在0.1至2%(重量),均以分解后的混合物数量为基准。为保证可能在酸催化剂情况下规定数量的催化剂,在碱性分解之后必须除去塔底的碱催化剂,但毕竟这或许过于昂贵,或必须在添加所需数量的酸催化剂之前,先用强酸将其中和。以这种方法确保有足够数量的活性酸存在。为本发明之目的起见,因此酸化就意味着将酸加至碱分解的釜残中,其数量既要中和其中所含碱催化剂,还要为此后酸分解提供足够数量的酸催化剂。
该催化剂,例如为被溶解或悬浮于酚中的,可连续计量加至流入分解反应塔的物流中。但也可通过一些中间容器,分批将它们预混为待分解的物料,再将此混合物连续输送至进行分解反应的塔内。
这些进行反应性精馏的塔相当于一般所用的蒸馏塔。在这些塔中,分解反应是紧靠着通过蒸馏和分馏方法将分解产物的酚及异亚烷基酚与未分解或不可分解化合物分离开来的过程而发生的。在此过程中,顶部流出分解产物,一般其纯度已足够下一步使用。不可分解的组分作为釜残而放出。对于本领域技术人员,反应性精馏是已知的,在乌尔曼工业化学百科全书,第五版,B4卷,第321-328页已有介绍。
对于本发明,适当缩小进行分解反应的塔下部直径,以适应分解反应过程中塔内由顶至底部的气液容积的减小,会有好处。在进行分解反应的塔内插入塔板,有利于保证塔内分解物料适宜的停留时间。这特别适用于其中进行分解反应的部分。在上部,采用填充体或填料有利于产物有效分离。当从第二分解塔蒸馏出酚的纯度不够双酚合成使用时,还可将它通过另外的塔或第一分解塔,使之进一步提纯。
生成双酚反应的优选方法是那些以可能最高的选择性产生双酚的方法。它们的特征在于,反应是在可能最低的酮浓度下进行。这可通过酚与酮及异亚烷基酚的反应在至少两个串联的内装酸性离子交换剂的反应器中实现,而且操作在尽可能低的温度,但随着温度的增加会使反应加速的条件下进行,这时酮及异亚烷基酚的总量在各个反应器间分配,并在将其加至各反应器之前使之在反应混合物中均匀分布。如果对酮及异烷烯基酚分布加以控制,双酚的选择性还可进一步提高,即要使各反应器温度越高,各台反应器中总量的份额越低,使该串联反应器操作于最大35至85℃的温度范围之内,优选38至75℃。
在各反应器之前,设置已知类型的混合单元和在通向催化剂床层的通路之前所需要的加热混合物的热交换器,分别保证酮及异亚烷基酚在原料酚及反应混合物中均匀分布,是有利的。
在其离开串联的最后一级的反应器和分离未反应酮之后,还可分离反应产物与酸性组分,如US-A4867341或EP-A552518所述,并还可使之通过精细过滤器,分离来自催化剂及装置的粉尘或其它固体污染物。然后反应混合物流入双酚合成常用的、本领域一般技术人员已知的一种结晶器中(见乌尔曼工业化学百科全书,第五版,B2卷,第3-1至3-34页;在US4209646中,例如可找到结晶方法),结晶出其中所含大部分的双酚(此时双酚A作为与酚的加成物),再经过滤分离,例如用旋转过滤机,并用酚加以洗涤。从与洗涤酚合并一起的母液中蒸馏出反应水及少量酚;蒸馏出的酚再经常规方法萃取加以分离。将水排出,将酚送回反应。在真空下就可完全从母液中蒸出酚。将所得残渣与碱催化剂混合,并连续计量加至反应性精馏中,使之在190至270℃下,优选200至260℃,更优选210至250℃和15至0.5毫巴,优选12至1毫巴,特别优选10至1毫巴下进行分解。将由酚、异亚烷基酚及其低聚物组成的馏出物送去反应。釜残经酸化后计量加入与前相同的第二反应性精馏中,于150至260℃,优选160至250℃,更优选170至240℃及上述压力下进行分解,并在分解过程中蒸馏出酚。此酚还可通过一个塔进一步纯化,再加至反应物流中。釜残从塔底抽出,送去处置。
由于双酚工厂较小的生产运行,如果由碱分解所得的釜残组分太少,对塔操作不经济,可将几次运行的这些少量东西合并一起,或将釜残收集在某一装置内,以形成大量釜残,然后在适宜装置中加以分解会有利的。
采用按照本发明的方法,如果从一开始就分出物料平衡中的不可避免的反应生成水,物料收率可高达98%之多。而且,还可得到特别纯的双酚。
离开串联反应器的反应混合物,在结晶之前可含双酚10至35%,优选12至32%及特别优选14至30%(重量)。如果含量对于结晶过程不适宜,可采用添加或蒸馏出酚的方法加以调节。
因此,与已知的双酚方法相比,按照本发明的方法具有生产非常纯的双酚,工艺十分简单、操作完全连续且收率极高的优点。
实施例(见附图1)
BPA按下述方法在三个串联的反应器中进行生产,反应器中装有酸性离子交换剂(SC102,贝尔公司),内含3.6%(重)的二甲基塞唑烷作为共催化剂。
将每小时5438重量份的酚,与每小时以数量为274重量份的三分之一的及402份的含酚及异亚烷基酚的分解产物,与每小时0.6kg/l催化剂的负荷量一起输送至处于50℃下的第一反应器中。所得反应产物经与另外每小时三分之一的上述量的丙酮及分解产物相混合,加热到60℃,并使之进入第二反应器。离开第二反应器后,将最后每小时三分之一的上述量的丙酮及分解产物混合至该反应产物中,加热到70℃,并将其加至第三反应器中。使所有的反应器负载速率维持在0.6kg/l·h。丙酮转化率为97至98%(重)。
由这种连续操作生产双酚A(BPA)的装置,用酸性离子交换剂进行催化,通过新鲜酚、来自酸及碱分解的酚、来自碱分解的丙酮及异亚烷基酚的反应,经蒸馏分离出残渣中的未反应丙酮(1)后,并还可通过一种过滤器及碱离子交换剂B进行过滤,用以分离出酸离子交换器沥滤出来的酸后,每产生6114重量份的反应混合产物,其组成I示于表1中。
按照通常的方法通过结晶(C)、负压过滤、用酚洗涤及进行压出(F)处理得到BPA-酚的加成物,再经真空(D)闪蒸酚之后,得出每小时983重量份的BPA,纯度99.78%。该过程形成的母液及洗涤酚经真空(2,3)连续蒸发;在经萃取(E)和分离水及萃取剂(6,7)后,蒸出的酚再部分重新送去反应,部分送去洗涤段;高沸残渣,经用0.5%(重量)的KOH在其中均匀分布后,作为熔融物II以每小时425重量份的速率计量加至具有20块塔板(4)的反应性精馏塔内,塔顶温度80至82℃,塔底温度238℃及操作压力2毫巴。在此反应性塔以为每小时376重量份的速率蒸出具有组成III的馏出物,并返回至反应,以生产BPA。釜残从塔底放出,速率每小时48重量份。往此熔融釜残中按所含每摩尔KOH加入2摩尔的甲苯磺酸,然后连续将其通入同样为20块塔板的反应性精馏塔(5)内,此塔在塔顶温度约73至76℃,塔底温度约205℃及压力5毫巴下操作。
所加材料的55%(重量)是从第二反应塔作为具有组成IV的馏出物蒸馏出,45%则从塔底放出,作为废渣处置。
在983份重的BPA的生产中,由此得到22份重的废渣,这相当于材料收率97.8%(在先抽出来自丙酮及酚缩合水之后)。
表1
o,o-BP | o,p-BP | 色满* | BPA | 茚满** | 三苯酚 | MG402 | NP | IPENP总和 | 酚 | 重量份/小时 | |
I | 0.09 | 5.06 | 0.22 | 93.72 | 0.16 | 0.60 | 0 | 0.14 | 0 | 0 | 6114 |
II | 0.19 | 16.10 | 0.51 | 75.76 | 0.20 | 2.10 | 0 | 1.22 | 0 | 3.91 | 425 |
III | 0.02 | 0.05 | 0.06 | 0.38 | 0.01 | 0.01 | 0 | 0.11 | 52.01 | 47.32 | 376 |
IV | 0.01 | 0.03 | 0.20 | 0.11 | 0.13 | 0 | 0 | 0.24 | 0 | 99.3 | 26 |
*色满为苯并二氢吡喃
**茚满为1,2-二氢化茚
Claims (1)
1.一种在至少两个串联的反应器中连续生产二羟基二芳基烷烃的方法,该方法包括:
(i)在第一反应器中使酚与至少部分酮及至少部分异烯基酚在尽可能低的温度进行反应形成反应混合物,在随后的至少一个反应器中于升高温度继续反应并向所述随后的至少一个反应器内至少加入部分剩余的酮和异烯基酚,以形成至少一种随后的反应混合物,
(ii)从反应混合物中蒸馏出并除去未反应的酮,
(iii)通过结晶从反应混合物中分离二羟基二芳基烷烃以获得母液和晶体,用洗涤酚洗涤如此获得的晶体,
(iv)合并所述母液与所述洗涤酚,蒸馏出酚并将其返回反应,
(v)在催化量的碱存在下,经第一反应性精馏使含二羟基二芳基烷烃、异构物的釜残分解,产生(a)离开塔顶部的酚及异烯基酚馏分和(b)在釜底馏出的高沸残液;
(vi)酸化所述高沸残液,使之含催化量的酸,并在第二反应性精馏中将所述残液分解成为(c)酚和(d)釜残,及
(vii)将(vi)中得到的酚和(v)中得到的馏分返回反应以生产二羟基二芳基烷烃。
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-
1998
- 1998-04-17 TW TW087105845A patent/TW448148B/zh active
- 1998-05-05 US US09/423,702 patent/US6307111B1/en not_active Expired - Fee Related
- 1998-05-05 DE DE59802737T patent/DE59802737D1/de not_active Expired - Fee Related
- 1998-05-05 AU AU77617/98A patent/AU7761798A/en not_active Abandoned
- 1998-05-05 WO PCT/EP1998/002643 patent/WO1998052895A1/de not_active Application Discontinuation
- 1998-05-05 EP EP98925534A patent/EP0984913B1/de not_active Expired - Lifetime
- 1998-05-05 JP JP54987398A patent/JP2001525831A/ja active Pending
- 1998-05-05 CN CN98804930A patent/CN1115317C/zh not_active Expired - Fee Related
- 1998-05-05 KR KR1019997010529A patent/KR20010012573A/ko not_active Application Discontinuation
- 1998-05-05 BR BR9809826-8A patent/BR9809826A/pt not_active IP Right Cessation
- 1998-05-05 ES ES98925534T patent/ES2167900T3/es not_active Expired - Lifetime
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Also Published As
Publication number | Publication date |
---|---|
US6307111B1 (en) | 2001-10-23 |
WO1998052895A1 (de) | 1998-11-26 |
EP0984913B1 (de) | 2001-11-21 |
DE59802737D1 (de) | 2002-02-21 |
CN1255112A (zh) | 2000-05-31 |
AU7761798A (en) | 1998-12-11 |
KR20010012573A (ko) | 2001-02-15 |
DE19720539A1 (de) | 1998-11-19 |
BR9809826A (pt) | 2000-06-20 |
JP2001525831A (ja) | 2001-12-11 |
ES2167900T3 (es) | 2002-05-16 |
TW448148B (en) | 2001-08-01 |
EP0984913A1 (de) | 2000-03-15 |
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