CN1043013C - Ion exchange recovery method of cobalt and manganese ions in acetic acid solution - Google Patents
Ion exchange recovery method of cobalt and manganese ions in acetic acid solution Download PDFInfo
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- CN1043013C CN1043013C CN93107509A CN93107509A CN1043013C CN 1043013 C CN1043013 C CN 1043013C CN 93107509 A CN93107509 A CN 93107509A CN 93107509 A CN93107509 A CN 93107509A CN 1043013 C CN1043013 C CN 1043013C
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000005342 ion exchange Methods 0.000 title claims abstract description 32
- 229910001437 manganese ion Inorganic materials 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000011084 recovery Methods 0.000 title abstract description 15
- 229910001429 cobalt ion Inorganic materials 0.000 title abstract description 11
- 239000010941 cobalt Substances 0.000 title description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 claims description 21
- 239000011572 manganese Substances 0.000 claims description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003456 ion exchange resin Substances 0.000 claims description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 3
- 239000003729 cation exchange resin Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract 4
- 238000010828 elution Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 4
- -1 aromatic carboxylic acids Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-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
- 238000003915 air pollution Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZBICJTQZVYWJPB-UHFFFAOYSA-N [Mn].[Co].[Br] Chemical compound [Mn].[Co].[Br] ZBICJTQZVYWJPB-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本发明是用离子交换的方法回收钴锰离子。The present invention recovers cobalt manganese ions by means of ion exchange.
液相空气催化氧化法是生产芳香基羧酸如苯二甲酸，偏苯三酸主要方法。在工业上广泛使用的钴-锰-溴催化体系，需要使用钴锰盐做为主催化剂，并加入溴化物做为助催化剂在醋酸溶液中进行反应。由于使用的金属盐尤其是钴盐价格很高，并在排放时会造成重金属离子对环境的污染，这就存在对钴锰离子回收问题。Liquid-phase air catalytic oxidation is the main method for producing aromatic carboxylic acids such as phthalic acid and trimellitic acid. The cobalt-manganese-bromine catalytic system widely used in industry needs to use cobalt-manganese salt as the main catalyst, and add bromide as the co-catalyst to react in the acetic acid solution. Due to the high price of metal salts used, especially cobalt salts, and the pollution of heavy metal ions to the environment when they are discharged, there is a problem of recycling cobalt and manganese ions.
美国Amoco公司回收催化剂的工艺是将生产过程中产生的残渣通过高温焚烧除去有机物，同时催化剂转变成相应的金属氧化物粉尘。用高压静电捕集此粉尘，之后再转化为催化剂所使用的盐类。但此法缺点耗能高，有大量的芳香基羧酸损失掉，对空气的污染比较大，回收及转化成盐的设备和过程复杂，回收成本高的缺点。美国专利US4,786,621公布的一种回收方法是：将残渣焚烧后，用醋酸溶解并加入还原剂还原溶解焚烧所得的粉尘，转变为催化剂盐类。但此法仍存在着焚烧时的耗能、芳香基羧酸损失及空气污染问题，并且回收钴锰盐催化剂存在精制困难，因而不得不采用较为复杂的方法，致使回收成本高。回收率也不高。The catalyst recycling process of Amoco Company in the United States is to incinerate the residue generated during the production process to remove organic matter, and at the same time, the catalyst is transformed into corresponding metal oxide dust. This dust is captured by high-voltage static electricity, and then converted into salts used in the catalyst. However, this method has the disadvantages of high energy consumption, loss of a large amount of aromatic carboxylic acid, relatively large air pollution, complicated equipment and process for recovery and conversion into salt, and high recovery cost. A recovery method disclosed in US Pat. No. 4,786,621 is as follows: after incinerating the residue, dissolve it with acetic acid and add a reducing agent to reduce and dissolve the incinerated dust to convert it into catalyst salts. However, this method still has the problems of energy consumption during incineration, loss of aromatic carboxylic acid, and air pollution, and it is difficult to recover the cobalt-manganese salt catalyst, so a more complicated method has to be adopted, resulting in high recovery costs. The recovery rate is not high either.
美国专利US4,298,759所公布的“通过水萃取后用离子交换方法从偏苯三酸生产过程中所得残渣中分离钴锰离子的方法”是将残渣用水溶解后形成水溶液，将此水溶解通过离子交换柱进行离子交换吸附其中的钴锰离子，脱离子后的溶液再进行其中所含芳香羧酸的回收。但本方法又带来了大量污水的处理问题，还需要增加很多设备和消耗大量能量，回收成本也很高。另外残渣是在芳香基羧酸精制过程中产生的，当有催化剂存在的情况下对芳香基羧酸进行精制，会引起一些副反应，对产品的质量和回收率都有不良影响。The "Method for Separating Cobalt and Manganese Ions from the Residue in Trimellitic Acid Production Process by Ion Exchange Method after Water Extraction" announced by U.S. Patent No. 4,298,759 is to dissolve the residue in water to form an aqueous solution, and dissolve the water to pass through the ion exchange method. The exchange column performs ion exchange to adsorb the cobalt and manganese ions, and the deionized solution is then recovered for the aromatic carboxylic acid contained therein. However, this method has brought about the problem of treating a large amount of sewage. It also needs to add a lot of equipment and consume a lot of energy, and the recovery cost is also very high. In addition, the residue is produced during the refining process of aromatic carboxylic acid. When the aromatic carboxylic acid is refined in the presence of a catalyst, some side reactions will be caused, which will have a negative impact on the quality and recovery of the product.
本发明的目的是提供一种直接从氧化产物过滤母液中用离子交换法吸附分离其中的钴锰离子的方法，使用这种方法可不改变原生产工艺流程，在芳香基羧酸精制前分离除去其中所含的金属离子，不会影响到其中所含芳香基羧酸的回收，并有助于提高芳香基羧酸主产品的产率和质量，节省能源，成本低。The purpose of the present invention is to provide a method for directly separating the cobalt and manganese ions from the oxidation product filtration mother liquor by ion exchange method, using this method can not change the original production process, and remove the aryl carboxylic acid before refining The contained metal ions will not affect the recovery of the aromatic carboxylic acid contained therein, and help to improve the yield and quality of the main product of the aromatic carboxylic acid, save energy and have low cost.
本发明是一种醋酸溶液中钴锰离子的离子交换回收方法，其特征在于它是将含有钴锰离子的醋酸溶液或将含有钴锰盐的芳香羧酸的固体溶解在醋酸溶液中，通过离子交换柱，使钴锰离子与离子交换柱中的强酸型阳离子交换树脂发生离子交换作用，钴锰离子吸附到离子交换柱中的离子交换树脂上，这时可将流出离子交换柱的不含钴锰离子的醋酸溶液收到容器里，再用无机酸或有机酸或者它们的盐来洗脱离子交换柱上吸附的钴锰，所使用的离子交换树脂为强酸型苯乙烯系阳离子交换树脂其中醋酸溶液中醋酸的含量重量浓度为20-100％，醋酸溶液中的钴锰离子与离子交换树脂上的氢离子进行交换，从而将钴锰离子交换吸附到树脂上，反应式为：The invention is an ion exchange recovery method for cobalt-manganese ions in acetic acid solution, which is characterized in that the acetic acid solution containing cobalt-manganese ions or the solid of aromatic carboxylic acid containing cobalt-manganese salts are dissolved in the acetic acid solution, and the ionic Exchange column, make cobalt manganese ion and strong acid type cation exchange resin in the ion exchange column ion exchange, cobalt manganese ion is adsorbed on the ion exchange resin in the ion exchange column, at this moment can flow out the cobalt-free ion exchange column The acetic acid solution of manganese ions is received in the container, and the cobalt and manganese adsorbed on the ion exchange column are eluted with inorganic acid or organic acid or their salts. The ion exchange resin used is a strong acid type styrene-based cation exchange resin. The weight concentration of acetic acid in the solution is 20-100%. The cobalt-manganese ions in the acetic acid solution are exchanged with the hydrogen ions on the ion-exchange resin, so that the cobalt-manganese ions are exchanged and adsorbed on the resin. The reaction formula is:
用本发明的方法回收钴锰，可以不改变原生产工艺流程，不影响所含芳香羧酸的回收，并有利于提高芳香基酸的主产品的质量，具有操作简单，回收率高，回收费用低，污染小等优点。Reclaiming cobalt manganese by the method of the present invention can not change the original production process, does not affect the recovery of the contained aromatic carboxylic acid, and is conducive to improving the quality of the main product of aromatic acid, and has the advantages of simple operation, high recovery rate and low recovery cost. Low, less pollution and other advantages.
实施例一：将组成为CoⅡ220.4PPm,MnⅡ154.2ppm,醋酸浓度为86％的固体物含量为7.2％醋酸溶液(偏三甲苯液相催化生产偏苯三甲酸的结晶洗涤母液)通过装有732离子交换树脂的离子交换柱。流出离子交换柱的2000毫升溶液，其中CoⅡ0PPm,MnⅡ0PPm。树脂上吸附的钴锰离子分别为484毫克和339毫克，金属离子脱除率＞99％。用5％盐酸100毫升可完全洗脱离子交换柱上吸附的钴锰离子，得到回收的钴锰盐溶液。Embodiment one: the composition is Co Ⅱ 220.4ppm, Mn Ⅱ 154.2ppm, and the solid content of acetic acid concentration is 86% and is 7.2% acetic acid solution (the crystallization washing mother liquor of trimellitic acid produced by trimellitic acid in liquid phase catalysis) through packing Ion exchange columns with 732 ion exchange resin. The 2000 milliliters solution flowing out of the ion exchange column, wherein Co Ⅱ 0PPm, Mn Ⅱ 0PPm. The cobalt and manganese ions adsorbed on the resin are respectively 484 mg and 339 mg, and the removal rate of metal ions is >99%. Using 100 ml of 5% hydrochloric acid can completely elute the cobalt-manganese ions adsorbed on the ion-exchange column to obtain recovered cobalt-manganese salt solution.
实施例二：将组成为CoⅡ15.0PPm,MnⅡ为24PPm，醋酸浓度为91.0％的溶液(对二甲苯液相催化氧化生产对苯二甲酸的结晶过滤母液)通过装有732离子交换树脂的离子交换柱。通过交换柱的20,000毫升溶液中，CoⅡ为0PPm,MnⅡ为0PPm，在用盐酸来洗脱离子交换柱上吸附的钴、锰离子得到回收的钴锰盐溶液。Embodiment two: the composition is Co Ⅱ 15.0PPm, Mn Ⅱ is 24PPm, and the solution of acetic acid concentration is 91.0% (p-xylene liquid-phase catalytic oxidation produces the crystallization and filtration mother liquor of terephthalic acid) through the 732 ion-exchange resin that is housed ion exchange column. In the 20,000 ml solution passing through the exchange column, Co II is 0PPm, Mn II is 0PPm, and the cobalt and manganese ions adsorbed on the ion exchange column are eluted with hydrochloric acid to obtain a recovered cobalt manganese salt solution.
实施例三：将生产偏苯三甲酸酐所剩的残渣100克，溶于1000毫升浓度为90％的醋酸中。所得溶液中钴含量为384PPm，锰含量为453PPm。将此溶液通过实施例1所用的离子交换树脂柱，流出液中钴锰的含量均为0PPm。交换到离子交换柱上的钴锰离子可用100毫升浓度为5％的盐酸完全洗脱，即可得到回收的钴锰盐溶液。Example 3: 100 grams of the remaining residue from the production of trimellitic anhydride was dissolved in 1000 milliliters of 90% acetic acid. The cobalt content in the obtained solution was 384PPm, and the manganese content was 453PPm. This solution is passed through the used ion exchange resin column of embodiment 1, and the content of cobalt manganese in the effluent is 0PPm. The cobalt-manganese ions exchanged on the ion-exchange column can be completely eluted with 100 ml of 5% hydrochloric acid to obtain a recovered cobalt-manganese salt solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93107509A CN1043013C (en) | 1993-06-24 | 1993-06-24 | Ion exchange recovery method of cobalt and manganese ions in acetic acid solution |
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|---|---|---|---|
| CN93107509A CN1043013C (en) | 1993-06-24 | 1993-06-24 | Ion exchange recovery method of cobalt and manganese ions in acetic acid solution |
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| Publication Number | Publication Date |
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| CN1088132A CN1088132A (en) | 1994-06-22 |
| CN1043013C true CN1043013C (en) | 1999-04-21 |
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| CN108947066A (en) * | 2018-07-13 | 2018-12-07 | 宁波永顺精细化工有限公司 | The recovery method of carboxylic acid and barium salt in carboxylic acid barium waste water |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4098867A (en) * | 1975-06-16 | 1978-07-04 | The Dow Chemical Company | Water-insoluble chelate exchange resins from aminopyridines and process for the selective extraction of valuable metals using the same |
| GB2020257A (en) * | 1978-04-10 | 1979-11-14 | Asahi Chemical Ind | Process for recovering heavy metal ions or heavy metal ions and halogen values from solutions comprising a lower aliphatic monocarboxylic acid |
| CN87106904A (en) * | 1986-10-14 | 1988-07-20 | 赫希斯特人造丝公司 | Regeneration method of carboxylation catalyst solution for removing corrosive metals |
| US5208194A (en) * | 1992-02-25 | 1993-05-04 | Arco Chemical Technology, L.P. | Recovery of group VIII transition metals from organic solutions using acidic ion-exchange resins |
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- 1993-06-24 CN CN93107509A patent/CN1043013C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4098867A (en) * | 1975-06-16 | 1978-07-04 | The Dow Chemical Company | Water-insoluble chelate exchange resins from aminopyridines and process for the selective extraction of valuable metals using the same |
| GB2020257A (en) * | 1978-04-10 | 1979-11-14 | Asahi Chemical Ind | Process for recovering heavy metal ions or heavy metal ions and halogen values from solutions comprising a lower aliphatic monocarboxylic acid |
| CN87106904A (en) * | 1986-10-14 | 1988-07-20 | 赫希斯特人造丝公司 | Regeneration method of carboxylation catalyst solution for removing corrosive metals |
| US5208194A (en) * | 1992-02-25 | 1993-05-04 | Arco Chemical Technology, L.P. | Recovery of group VIII transition metals from organic solutions using acidic ion-exchange resins |
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