[go: up one dir, main page]

CN1067975C - 氯丁烯羰基化转化为戊烯酰氯中催化剂的回收 - Google Patents

氯丁烯羰基化转化为戊烯酰氯中催化剂的回收 Download PDF

Info

Publication number
CN1067975C
CN1067975C CN95192918A CN95192918A CN1067975C CN 1067975 C CN1067975 C CN 1067975C CN 95192918 A CN95192918 A CN 95192918A CN 95192918 A CN95192918 A CN 95192918A CN 1067975 C CN1067975 C CN 1067975C
Authority
CN
China
Prior art keywords
palladium
product
distillation
hcl
chloride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN95192918A
Other languages
English (en)
Other versions
CN1148378A (zh
Inventor
B·E·默弗里
E·E·布奈尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dsm Co ltd
EIDP Inc
Original Assignee
Dsm Co ltd
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dsm Co ltd, EI Du Pont de Nemours and Co filed Critical Dsm Co ltd
Publication of CN1148378A publication Critical patent/CN1148378A/zh
Application granted granted Critical
Publication of CN1067975C publication Critical patent/CN1067975C/zh
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2291—Olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/40—Regeneration or reactivation
    • B01J31/4015—Regeneration or reactivation of catalysts containing metals
    • B01J31/4023—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper
    • B01J31/4038—Regeneration or reactivation of catalysts containing metals containing iron group metals, noble metals or copper containing noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/34—Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/824—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/08—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/25—Nitrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J27/26—Cyanides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

从蒸馏尾料中回收钯催化剂残渣，其方法是用盐酸处理该蒸馏尾料，将钯组分转化为丁烯基氯化钯，以及使用此丁烯基氯化钯作为氯丁烯羰基化转化为3-戊烯酰氯的催化剂。

Description

氯丁烯羰基化转化为戊烯酰氯中催化剂的回收
发明领域
本发明涉及氯丁烯的羰基化制备戊烯酰氯的方法中钯催化剂的回收和再循环。
发明背景
Bunel等人的美国专利5,288,903公开了使用钯催化剂通过氯丁烯的羰基化来制备戊烯酰氯。在实例1中产物混合物进行蒸馏和含在尾料中的催化剂仍可循环返回羰基化步骤。
发明概述
本发明是3-戊烯酰氯的制备方法，包括：(a)在100～120℃的温度下用浓盐酸处理蒸馏尾料，该尾料是从含钯催化剂残渣的反应混合物进行3-戊烯酰氯的蒸馏所得到的，(b)将步骤a的产物与氯丁烯合并，(c)使步骤b的产物形成两相，即一有机相和一含钯催化剂残渣的盐酸相，(d)将步骤c得到的两相分离，(e)将步骤d得到的盐酸相与氯丁烯合并，(f)在约70～75℃温度下在一氧化碳氛围中蒸馏步骤e的产物，一种共沸混合物，直到仅观测到一相，即含有氯丁烯和同时生成的巴豆基氯化钯的一相，(g)在压力约为1.72～34.47MPa(250～5000磅/英寸2)的一氧化碳氛围中和在约90～190℃温度下加热含有氯丁烯和巴豆基氯化钯的步骤f的产物，和(h)通过蒸馏从步骤g的产物中回收3-戊烯酰氯。在步骤h之后还遗留有蒸馏尾料，这尾料可以循环回步骤a。优选地，步骤f和g之间可以对步骤f的产物进行干燥。
发明详述
一开始形成含3-戊烯酰氯的混合物所使用的钯催化剂可以是钯的一些化合物的混合物。从上述的含3-戊烯酰氯的混合物通过蒸馏回收3-戊烯酰氯并留下含钯的蒸馏尾料。适宜的钯化合物包括：一般说来：所有零价、二价或三价的Pd化合物都是适合的起始催化剂。
如下的例子有：
卤化钯(PdCl2,PdBr2,PdI2,Na2PdCl4等)
硫酸钯
硝酸钯
羰酸钯盐(醋酸钯等)
磺酸钯
有机钯的配合物(乙酰丙酮钯，双(联亚苄基丙酮)钯等)
吡啶和吡啶类钯配合物
烯丙基卤化钯，特别是巴豆基氯化钯的二聚物
氰化钯
零价和二价钯的烷基和芳基膦配合物(四[三苯基膦]钯，二[三苯基膦]钯二氯化物等)
钯黑
载体上的钯或其化合物(载于氧化铝，氧化硅，粘土，硫酸盐，碳酸盐，树脂，聚合物等上的钯
氧化钯
从氯丁烯生成3-戊烯酰氯与钯催化剂残渣的混合物的初始反应条件可以是如美国专利5,288,903中所述的方法。
在步骤f和g之间进行的干燥步骤，优选地可以使用分子筛，但是也可以使用其它干燥方法，如加入水的吸收剂、吸附剂和干燥剂。
在实例中描述的尾料是按下述得到的：
向两个串联的50毫升连续搅拌桶式反应器中通入含有1379.16克氯丁烯和3.84克[巴豆基-Pd-Cl]2的溶液和CO，其进料比为0.57摩尔CO/摩尔氯丁烯。反应器的温度为120℃和CO压力为13.78MPa(2000psig)以及停留时间2小时。在CO的气氛下收集产物。含有3-戊烯酰氯、氯丁烯和催化剂的溶液，在减压下进行蒸馏，收取氯丁烯和部分3-戊烯酰氯塔顶馏出物。将蒸馏尾料用氯丁烯稀释至与初始进料相同的体积，然后在同样条件下再通入反应器中。此循环再重复13次。下表给出每次循环的条件和每次循环生成的3-戊烯酰氯的量。
  循环   蒸馏压力(mmHg) 最终容器温度(℃) 送入蒸馏的3PACl克数 塔顶馏出物3PACl克数
    1     200     85     397.2     166.0
    2     200     92     483.6     258.4
    3     200     108     502.4     465.4
    4     200     139     412.0     312.8
    5     500     119     407.2     95.2
    6     750     122     531.7     119.8
    7     200     118     601.7     521.8
    8     150     114     405.3     363.0
    9     150     114     394.3     367.6
    10     150     104     276.4     237.8
    11     150     122     272.2     246.2
    12     150     117     336.7     294.0
    13     150     125     351.5     331.0
13次循环之后，按实例1所述处理所得55.7克尾料。实例1
55.7克蒸馏尾料([Pd]=5779ppm)与8毫升水和100毫升HCl(37％)合并，在105℃加热2.5小时。在25℃下冷却，加入100毫升氯丁烯。有机相与HCl相(105克)分离。钯在HCl相的浓度为2139ppm。
在25℃经旋转蒸发来浓缩有机相，然后与100毫升HCl(37％)合并，在105℃加热2小时。混合物冷却至25℃之后，加入100毫升氯丁烯。有机相与HCl相(103克)分离。钯在HCl相的浓度为302ppm。
在25℃经旋转蒸发来浓缩有机相，然后与100毫升HCl(37％)合并，在105℃加热2小时。混合物冷却至25℃之后，加入100毫升氯丁烯。有机相与HCl相(94.8克)分离。钯在HCl相的浓度为67ppm。
在一装有迪安-斯达克装置的2升圆底烧瓶中使上述得到的HCl溶液与500毫升氯丁烯合并。一喷射管插入液体中，以保持蒸馏中的一氧化碳气氛。在72℃收集两相蒸馏物(氯丁烯和浓HCl)。收集270克HCl后，停止蒸馏。氯丁烯溶液冷却至25℃和用10克4A分子筛干燥。
含催化剂的60克氯丁烯溶液送入100毫升高压釜中，在一氧化碳(总压为5.86MPa(850psig))气氛下在125℃下加热3小时：GC分析表明：生成3-戊烯酰氯，和氯丁烯向3-戊烯酰氯的转化率为18.8％(摩尔)。

Claims (3)

1．制备3-戊烯酰氯的方法，包括：(a)在100～120℃的温度用浓HCl处理蒸馏尾料，该尾料是从含钯催化剂残渣的反应混合物进行3-戊烯酰氯蒸馏所得的，(b)将步骤a的产物与氯丁烯合并，(c)使步骤b的产物形成两相，即一有机相和一含钯催化剂的HCl相，(d)将步骤c得到的两相分离，(e)将步骤d得到的HCl相与氯丁烯合并，(f)在70～75℃温度下在一氧化碳氛围蒸馏步骤e的产物，一种共沸混合物，直到仅观测到一相，即含有氯丁烯和同时生成的巴豆基氯化钯的一相，(g)在压力为1.72～34.47MPa的一氧化碳氛围和在90～190℃温度下加热含有氯丁烯和巴豆基氯化钯的步骤f的产物，和(h)通过蒸馏从步骤g的产物中回收3-戊烯酰氯。
2．权利要求1的方法，其中在步骤(h)之后还遗留有蒸馏尾料，并将此尾料再循环回步骤(a)。
3．权利要求1的方法，其中在步骤f的产物按步骤g处理前先进行干燥。
CN95192918A 1994-05-04 1995-05-03 氯丁烯羰基化转化为戊烯酰氯中催化剂的回收 Expired - Fee Related CN1067975C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/237,983 1994-05-04
US08/237,983 US5399753A (en) 1994-05-04 1994-05-04 Catalyst recovery in the carbonylation of chlorobutenes to pentenoyl chloride

Publications (2)

Publication Number Publication Date
CN1148378A CN1148378A (zh) 1997-04-23
CN1067975C true CN1067975C (zh) 2001-07-04

Family

ID=22896013

Family Applications (1)

Application Number Title Priority Date Filing Date
CN95192918A Expired - Fee Related CN1067975C (zh) 1994-05-04 1995-05-03 氯丁烯羰基化转化为戊烯酰氯中催化剂的回收

Country Status (8)

Country Link
US (1) US5399753A (zh)
EP (1) EP0758311B1 (zh)
JP (1) JPH10500108A (zh)
CN (1) CN1067975C (zh)
CA (1) CA2188553A1 (zh)
DE (1) DE69511857T2 (zh)
TW (1) TW314510B (zh)
WO (1) WO1995030637A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0791393A1 (en) 1996-02-23 1997-08-27 E.I. Du Pont De Nemours And Company Palladium catalyst recovery

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992016476A2 (en) * 1991-03-18 1992-10-01 E.I. Du Pont De Nemours And Company Process for the manufacture of adipic acid

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2627360A (en) * 1949-04-01 1953-02-03 Goodrich Co B F Hollow article
GB987274A (en) * 1962-08-31 1965-03-24 Ici Ltd Improvements in and relating to the production of halides of unsaturated aliphatic acids or derivatives thereof
GB1080867A (en) * 1963-07-26 1967-08-23 Shell Int Research A process for the preparation of carboxylic acids and derivatives thereof
US3309403A (en) * 1963-10-16 1967-03-14 Nat Distillers Chem Corp Carbonylation of allylic halides
US3338961A (en) * 1964-01-30 1967-08-29 Ethyl Corp Promoted catalytic carbonylation of allylic halides
US3691043A (en) * 1965-09-09 1972-09-12 Exxon Research Engineering Co Preparation of acid halides from paraffins
US3423456A (en) * 1966-01-10 1969-01-21 Nat Distillers Chem Corp Reaction of allylic halides in the vapor phase with carbon monoxide to form 3-enoyl halides
US3626005A (en) * 1967-07-14 1971-12-07 Nat Distillers Chem Corp Preparation of unsaturated acyl halides
US3536739A (en) * 1967-10-19 1970-10-27 Nat Distillers Chem Corp Reaction of allyl derivatives with carbon monoxide and 1,3 - dienic olefins
US3627827A (en) * 1968-11-14 1971-12-14 Nat Distillers Chem Corp Reaction of allylic halides with carbon monoxide and acetylene
DE3035201A1 (de) * 1980-09-18 1982-04-29 Hoechst Ag, 6000 Frankfurt Verfahren zur herstellung von carbonsaeurehalogeniden
US4749525A (en) * 1986-07-02 1988-06-07 Ashland Oil, Inc. Process for the carbonylation of propylene

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992016476A2 (en) * 1991-03-18 1992-10-01 E.I. Du Pont De Nemours And Company Process for the manufacture of adipic acid

Also Published As

Publication number Publication date
WO1995030637A1 (en) 1995-11-16
CN1148378A (zh) 1997-04-23
CA2188553A1 (en) 1995-11-16
TW314510B (zh) 1997-09-01
US5399753A (en) 1995-03-21
EP0758311A1 (en) 1997-02-19
EP0758311B1 (en) 1999-09-01
DE69511857T2 (de) 2000-04-13
JPH10500108A (ja) 1998-01-06
DE69511857D1 (de) 1999-10-07

Similar Documents

Publication Publication Date Title
CA2434720C (en) Low energy carbonylation process
EP0497521B1 (en) Removal of carbonyl impurities from a carbonylation process stream
TWI422612B (zh) 聚對苯二甲酸乙二酯（ｐｅｔ）之醇解作用以形成對苯二甲酸二乙酯（ｄｅｔ）及ｄｅｔ之氧化作用
TWI382868B (zh) 蒸餾方法
CN1131849C (zh) 制备1,1,1,3,3－五氯丁烷的方法
CN1201446A (zh) 生产二氟甲烷的方法
EP1549602A2 (en) Process for producing carboxylic acid and system for producing the same
JP2006509025A (ja) 乳酸エチルの連続製造方法
JPS604151A (ja) テレフタル酸ジエステルの製造方法
CN1835915A (zh) 制备并分离二腈化合物的方法
CN1067975C (zh) 氯丁烯羰基化转化为戊烯酰氯中催化剂的回收
DE69710148T2 (de) Verfahren zum Herstellen von Diarylcarbonat
CN1131198C (zh) 粗品液态乙酸乙烯酯的分离方法
CN1266444A (zh) 低比色指数聚四氢呋喃的制备方法
DE69416753T2 (de) Herstellung von 3-Pentensäure und Katalysator dafür
JP3581725B2 (ja) アセトアルデヒドとヨウ化メチルの分離方法
CN1192707A (zh) 钯催化剂的分离方法
CN1551865A (zh) 制备2,6-萘二羧酸的方法
CN1335291A (zh) 1,1,1,3,3－五氯丙烷的制备方法
CN1133679C (zh) 制备聚酯和山梨酸的方法
JPH09157233A (ja) カルボン酸アミドの製造方法
JPWO1994000410A1 (ja) アルカジエノール類の製造方法
CN1285552C (zh) 1,1,1,3,3—五氯丁烷的制备方法
JPH09227420A (ja) アルキルハロゲン化物の製法
US6133477A (en) Preparation of 3-pentenoic acid

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee