CN112851496A - 一种对甲基苯甲酸的制备方法 - Google Patents
一种对甲基苯甲酸的制备方法 Download PDFInfo
- Publication number
- CN112851496A CN112851496A CN202011601414.1A CN202011601414A CN112851496A CN 112851496 A CN112851496 A CN 112851496A CN 202011601414 A CN202011601414 A CN 202011601414A CN 112851496 A CN112851496 A CN 112851496A
- Authority
- CN
- China
- Prior art keywords
- toluic acid
- bromine
- xylene
- acid according
- catalyst
- 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.)
- Pending
Links
- LPNBBFKOUUSUDB-UHFFFAOYSA-N p-toluic acid Chemical compound CC1=CC=C(C(O)=O)C=C1 LPNBBFKOUUSUDB-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 5
- 239000010941 cobalt Substances 0.000 claims abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- -1 transition metal salts Chemical class 0.000 claims abstract description 3
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007800 oxidant agent Substances 0.000 claims abstract 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical group [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 4
- KMTDMTZBNYGUNX-UHFFFAOYSA-N 4-methylbenzyl alcohol Chemical compound CC1=CC=C(CO)C=C1 KMTDMTZBNYGUNX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MNRIMQGAYZTPNJ-UHFFFAOYSA-N [N+](=O)(O)[O-].CC1=CC=C(C=C1)C(C)C Chemical compound [N+](=O)(O)[O-].CC1=CC=C(C=C1)C(C)C MNRIMQGAYZTPNJ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N ethyl formate Chemical compound CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/255—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting
- C07C51/265—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of compounds containing six-membered aromatic rings without ring-splitting having alkyl side chains which are oxidised to carboxyl groups
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明涉及一种对甲基苯甲酸的制备方法,其特征在于,以对二甲苯为起始原料,以空气为氧化剂,在无溴催化剂存在下在氧化塔中进行气相氧化合成。所述无溴催化剂选自钴、锰、铈等具有催化活性的过渡金属盐类或其组合物。本发明方法克服了常规方法中使用溴化物作为催化剂的缺陷,选择性好,反应收率高,产品纯度高,是一种既经济又环境友好的对甲基苯甲酸的制备方法。
Description
技术领域
本发明属于精细化工领域,具体涉及一种对甲基苯甲酸的制备方法。
背景技术
对甲基苯甲酸是一种重要的化学中间体,广泛地用于医药、感光材料、农药、有机颜料、荧光增白剂等的合成。其制备方法主要有对二甲苯或对甲基异丙苯硝酸氧化法、对二甲苯空气氧化法、甲苯羰基化-氧化法、电合成法等,其中对二甲苯空气氧化法具有突出的环境友好和原料廉价易得优势,最具应用前景。
目前对二甲苯空气氧化法一般采用鈷、锰与溴化物组成的三元催化系统,虽然溴的使用有利于气态氧化作用,但是氧化过程中产生的溴乙酸属于高腐蚀性物质,需要使用衬有高价鈦的特殊装置。此外,反应过程中还产生溴化甲烷,是危险化学品。
另外,该方法还存在反应条件苛刻、转化率和产品选择性较低等种种缺陷。
发明内容
为克服现有技术中对二甲苯空气氧化合成对甲基苯甲酸方法的种种缺陷,本发明锐意探索,研发出了一种无溴催化剂以替代传统的鈷、锰与溴化物组成的三元催化系统,并进一步开发了一种新的对甲基苯甲酸的制备方法。
根据本发明的方法,将对二甲苯和无溴催化剂计量,投入反应塔,通入空气进行反应,生成对甲基苯甲酸;然后热过滤去掉副产物对苯二甲酸,生成对甲基苯甲酸和未反应的原料进行蒸馏回收原料再利用,蒸馏余液再进行减压蒸馏蒸出产品对甲基苯甲酸。
根据本发明,所述无溴催化剂选自钴、锰、铈等具有催化活性的过渡金属盐类或其组合物,优选乙酸钴、乙酸锰、乙酸铈及其组合物。其用量相对于1摩尔对二甲苯为1-200毫摩尔,优选10-100毫摩尔。
根据本发明,反应温度为100-200℃,优选120-150℃,最优选120-125℃。
根据本发明,氧化反应收率可达90%以上,最高可达99%,副反应约为2.4%。
根据本发明的一种对甲基苯甲酸的制备方法,不使用溴化物作为催化剂气态氧化对二甲苯以制造对甲苯甲酸为主要产物的方法,催化剂的选择性好,反应收率高,产品纯度高,不仅仅有极高经济效益与商业潜力,同时是一种环境友好的工业技术。
具体实施方式
本发明下面将结合具体实施例作进一步详细说明。本领域技术人员应当懂得,本申请并不仅限于该具体实施例中,以下实施例仅用于说明本发明,并不是对本发明的限定。
实施例1
将300克对二甲苯通过计量罐计量,用泵送至氧化塔,同时将催化剂5.0克乙酸鈷投加至氧化塔中,升温至110℃(蒸汽间接加热),通入空气控制反应温度125℃、压力0.35Mpa,反应结束后,反应物通过空气压送至蒸苯釜进行蒸对二甲苯、精馏等后续操作。
反应物通过气相色谱法分析,结果表明对二甲苯的转化为97.5%,其中组分为:对甲苯甲酸(PTA)为82.39%,对甲基苯甲醛为1.82%,对甲基苯甲醇为13.50%,其它为1.35%。
实施例2
300克对二甲苯于120℃、在4.4克乙酸钴与0.3克乙酸铈作为催化剂被氧化。反应如实施例1中实施。95.0%的对二甲苯转化为氧化化合物,其中含有对甲苯甲酸(PTA)96.62%,对甲基苯甲醛0.42%与对甲基苯甲醇2.96%。
实施例3
300克对二甲苯于122℃、在4.48克乙酸锰与0.31克乙酸铈作为催化剂被氧化。反应如实施例1中实施。99.0%的对二甲苯转化为氧化化合物,其中含有对甲苯甲酸(PTA)84.68%,对甲基苯甲醛2.04%与对甲基苯甲醇13.22%。
Claims (8)
1.一种对甲基苯甲酸的制备方法,其特征在于,以对二甲苯为起始原料,以空气为氧化剂,在无溴催化剂存在下在氧化塔中进行气相氧化合成。
2.根据权利要求1的一种对甲基苯甲酸的制备方法,所述无溴催化剂选自钴、锰、铈等具有催化活性的过渡金属盐类或其组合物。
3.根据权利要求2的一种对甲基苯甲酸的制备方法,所述无溴催化剂为乙酸钴、乙酸锰、乙酸铈及其组合物。
4.根据权利要求2的一种对甲基苯甲酸的制备方法,所述无溴催化剂的用量相对于1摩尔对二甲苯为1-200毫摩尔。
5.根据权利要求4的一种对甲基苯甲酸的制备方法,所述无溴催化剂的用量相对于1摩尔对二甲苯为10-100毫摩尔。
6.根据权利要求1的一种对甲基苯甲酸的制备方法,反应温度为100-200℃。
7.根据权利要求6的一种对甲基苯甲酸的制备方法,反应温度为120-150℃。
8.根据权利要求6的一种对甲基苯甲酸的制备方法,反应温度为120-125℃。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011601414.1A CN112851496A (zh) | 2020-12-30 | 2020-12-30 | 一种对甲基苯甲酸的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202011601414.1A CN112851496A (zh) | 2020-12-30 | 2020-12-30 | 一种对甲基苯甲酸的制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN112851496A true CN112851496A (zh) | 2021-05-28 |
Family
ID=75998335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202011601414.1A Pending CN112851496A (zh) | 2020-12-30 | 2020-12-30 | 一种对甲基苯甲酸的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN112851496A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114507128A (zh) * | 2022-02-17 | 2022-05-17 | 吴桥县六合德利化工有限责任公司 | 对甲基苯甲酸精制工艺 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060247464A1 (en) * | 2005-03-22 | 2006-11-02 | Saxena Mahendra P | Process for the preparation of p-toluic acid by liquid phase oxidation of p-xylene in water |
CN101146755A (zh) * | 2005-03-31 | 2008-03-19 | 科学与工业研究委员会 | 通过对-二甲苯在水中的液相氧化来制备对-甲苯甲酸的方法 |
CN101437610A (zh) * | 2006-05-08 | 2009-05-20 | Bp北美公司 | 在水中生产芳香羧酸的方法 |
-
2020
- 2020-12-30 CN CN202011601414.1A patent/CN112851496A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060247464A1 (en) * | 2005-03-22 | 2006-11-02 | Saxena Mahendra P | Process for the preparation of p-toluic acid by liquid phase oxidation of p-xylene in water |
CN101146755A (zh) * | 2005-03-31 | 2008-03-19 | 科学与工业研究委员会 | 通过对-二甲苯在水中的液相氧化来制备对-甲苯甲酸的方法 |
CN101437610A (zh) * | 2006-05-08 | 2009-05-20 | Bp北美公司 | 在水中生产芳香羧酸的方法 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114507128A (zh) * | 2022-02-17 | 2022-05-17 | 吴桥县六合德利化工有限责任公司 | 对甲基苯甲酸精制工艺 |
CN114507128B (zh) * | 2022-02-17 | 2023-10-03 | 吴桥县六合德利化工有限责任公司 | 对甲基苯甲酸精制工艺 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU732522B2 (en) | Method to produce aromatic carboxylic acids | |
US2723994A (en) | Oxidation of xylene and toluic acid mixtures to phthalic acids | |
CN105873890A (zh) | 用于制备纯化的羧酸的氧化方法 | |
CN112851496A (zh) | 一种对甲基苯甲酸的制备方法 | |
CN102452894B (zh) | 一种纳米β分子筛催化氧化环酮的方法 | |
US2963509A (en) | Process for oxidation of mono-alkyl benzene | |
JP5055262B2 (ja) | 水中におけるp−キシレンの液相酸化によるp−トルイル酸の製造方法 | |
US4902827A (en) | Process for the preparation of adipic acid | |
JP3715492B2 (ja) | トルエンの触媒液相空気酸化によるベンズアルデヒドの改良された製造方法 | |
CN101830783A (zh) | 一种希夫碱配合物催化氧气氧化醇制备醛的方法 | |
US6344586B1 (en) | Process for producing adipic acid | |
EP1088810B1 (en) | Process for the production of benzaldehyde by the catalytic liquid phase air oxidation of toluene | |
WO2021255671A1 (en) | Method for producing aromatic dicarboxylic acid using iron co‑catalyst | |
US2963508A (en) | Process for oxidation of monoalkyl naphthalene | |
JPH07196573A (ja) | アセトフェノンの製造法 | |
US4980501A (en) | Production of secondary-butyl fluoroester and secondary-butyl alcohol obtained therefrom | |
TWI264432B (en) | Process for the production of terephthalic acids | |
US7598415B2 (en) | Process for the preparation of p-toluic acid by liquid phase oxidation of p-xylene in water | |
JPS5929170B2 (ja) | β−フエニルエチルアルコ−ルおよび酢酸β−フエニルエチルの製造方法 | |
US3703547A (en) | Method of preparing phthalic acids | |
US7709681B2 (en) | Process for the production of trimellitic acid | |
KR101642960B1 (ko) | 벤조산의 제조 방법 | |
JPH11335319A (ja) | α−ヒドロキシカルボン酸の製造方法 | |
EP4157818A1 (en) | A process for the oxidation of primary alcohols to carboxylic acids | |
CN117443446A (zh) | 甲苯制对甲酚的催化剂的制备方法和对甲酚的制备方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210528 |