CN1129556C - Treatment and source recovering method for waste water of 1,4-dihydroxy anthraquinone produetion - Google Patents
Treatment and source recovering method for waste water of 1,4-dihydroxy anthraquinone produetion Download PDFInfo
- Publication number
- CN1129556C CN1129556C CN00112386.6A CN00112386A CN1129556C CN 1129556 C CN1129556 C CN 1129556C CN 00112386 A CN00112386 A CN 00112386A CN 1129556 C CN1129556 C CN 1129556C
- Authority
- CN
- China
- Prior art keywords
- tower
- dihydroxyanthraquinone
- adsorption
- phthalic acid
- concentration
- 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
Links
- GUEIZVNYDFNHJU-UHFFFAOYSA-N quinizarin Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(O)=CC=C2O GUEIZVNYDFNHJU-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000002351 wastewater Substances 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 15
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000001179 sorption measurement Methods 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 11
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003480 eluent Substances 0.000 claims abstract description 4
- 238000010828 elution Methods 0.000 claims abstract description 3
- 238000003795 desorption Methods 0.000 claims description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000005416 organic matter Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 3
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229960001156 mitoxantrone Drugs 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000005429 filling process Methods 0.000 claims 1
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 abstract 1
- -1 anthraquinone compounds Chemical class 0.000 abstract 1
- 238000007334 copolymerization reaction Methods 0.000 abstract 1
- 235000019253 formic acid Nutrition 0.000 abstract 1
- 230000020477 pH reduction Effects 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- BTLXPCBPYBNQNR-UHFFFAOYSA-N 1-hydroxyanthraquinone Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2O BTLXPCBPYBNQNR-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920001429 chelating resin Polymers 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- JCMUOFQHZLPHQP-UHFFFAOYSA-N L-L-Ophthalmic acid Natural products OC(=O)CNC(=O)C(CC)NC(=O)CCC(N)C(O)=O JCMUOFQHZLPHQP-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- JPICKYUTICNNNJ-UHFFFAOYSA-N anthrarufin Chemical compound O=C1C2=C(O)C=CC=C2C(=O)C2=C1C=CC=C2O JPICKYUTICNNNJ-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- JCMUOFQHZLPHQP-BQBZGAKWSA-N ophthalmic acid Chemical compound OC(=O)CNC(=O)[C@H](CC)NC(=O)CC[C@H](N)C(O)=O JCMUOFQHZLPHQP-BQBZGAKWSA-N 0.000 description 1
- HVVLQPOCRDLFGA-UHFFFAOYSA-N ophthalmic acid Natural products CCC(NC(=O)C(N)CCC(=O)O)C(=O)NCC(=O)O HVVLQPOCRDLFGA-UHFFFAOYSA-N 0.000 description 1
- 108010088490 ophthalmic acid Proteins 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Water Treatment By Sorption (AREA)
Abstract
本发明公开了一种1，4-二羟基蒽醌生产废水的治理与资源回收利用方法，它是将废水在0～60℃以0.5～7BV/h的流量通过苯乙烯-二乙烯基苯共聚大孔吸附树脂柱，废水中的邻苯二甲酸和少量蒽醌类化合物被吸附在大孔树脂上，用0.5～4mol/L的氢氧化钠溶液在20～95℃，以0.2～3.0BV/h流量洗脱，将树脂再生处理，同时洗脱液酸化后回收邻苯二甲酸，用本方法处理，出水无色透明CODcr降至100mg/L以下，去除率为99.5%以上，邻苯二甲酸的去除率为99.5%以上，回收率达90%以上，回收晶体纯度为97.9-99.6%，1，4-二羟基蒽醌的去除率为100%。The invention discloses a method for the treatment and resource recycling of 1,4-dihydroxyanthraquinone production wastewater, which is to pass the wastewater through styrene-divinylbenzene copolymerization at a flow rate of 0.5-7BV/h at 0-60°C Macroporous adsorption resin column, phthalic acid and a small amount of anthraquinone compounds in the wastewater are adsorbed on the macroporous resin, using 0.5~4mol/L sodium hydroxide solution at 20~95℃, at 0.2~3.0BV/ h flow rate elution, resin regeneration treatment, and recovery of phthalic acid after acidification of the eluent at the same time, treated with this method, the colorless and transparent COD cr of the effluent is reduced to below 100mg/L, and the removal rate is more than 99.5%. The removal rate of formic acid is over 99.5%, the recovery rate is over 90%, the purity of recovered crystals is 97.9-99.6%, and the removal rate of 1,4-dihydroxyanthraquinone is 100%.
Description
一、技术领域1. Technical field
本发明涉及蒽醌染料及中间体1，4-二羟基蒽醌生产废水的治理，具体地说，是1，4-二羟基蒽醌生产废水中邻苯二甲酸的回收利用和其它有机物的去除。The present invention relates to the treatment of anthraquinone dyes and intermediate 1,4-dihydroxyanthraquinone production wastewater, specifically, the recycling of phthalic acid and the removal of other organic matter in 1,4-dihydroxyanthraquinone production wastewater .
二、背景技术2. Background technology
1，4-二羟基蒽醌是一种重要的染料中间体，其本身也是一种重要的染料。目前国内主要采用传统的以对苯二酚为原料的合成路线或以对氯苯酚为原料合成路线，生产1吨1，4-二羟基蒽醌要排放60～96吨的深红色废水，CODCr高达7000～24000mg/L，其中主要含有4700～12000mg/L的邻苯二甲酸以及少量的1，4-二羟基蒽醌、1，5-二羟基蒽醌等产物及其副产物，另外还含有0.5～20％的硫酸和少量的硼酸。1,4-Dihydroxyanthraquinone is an important dye intermediate, and it is also an important dye itself. At present, the traditional synthetic route using hydroquinone as raw material or the synthetic route using p-chlorophenol as raw material is mainly adopted in China. To produce 1 ton of 1,4-dihydroxyanthraquinone, 60-96 tons of dark red wastewater, COD Cr As high as 7000-24000mg/L, which mainly contains 4700-12000mg/L phthalic acid and a small amount of 1,4-dihydroxyanthraquinone, 1,5-dihydroxyanthraquinone and other products and their by-products, and also contains 0.5-20% sulfuric acid and a small amount of boric acid.
文献检索结果表明，已有的国内外文献报道中未涉及1，4-二羟基蒽醌生产废水的治理与资源回收利用。The results of literature search showed that the treatment and resource recovery of 1,4-dihydroxyanthraquinone production wastewater were not involved in the existing domestic and foreign literature reports.
三、发明内容3. Contents of the invention
本发明的目的是提供一种技术，不仅能有效治理1，4-二羟基蒽醌生产废水，去除其中绝大部分有机物，还能富集回收其中流失的有机化工原料邻苯二甲酸，实现废水治理与资源回收利用的统一。The purpose of the present invention is to provide a technology that can not only effectively control 1,4-dihydroxyanthraquinone production wastewater, remove most of the organic matter, but also enrich and recycle the lost organic chemical raw material phthalic acid, so as to realize the production of wastewater Harmonization of governance and resource recycling.
本发明的技术方案如下：Technical scheme of the present invention is as follows:
一种1，4-二羟基蒽醌生产废水的治理与资源回收利用方法，它是将生产废水进行预处理，即对于含1，4-二羟基蒽醌低于10mg/L的废水，预处理为直接过滤，对于含1，4-二羟基蒽醌高于10mg/L的废水，先调节PH至3-4，再过滤，去除其中的1，4-二羟基蒽醌和悬浮物，以保证治理过程中树脂的吸附效率，同时提高回收邻苯二甲酸的纯度，然后将经过预处理的生产废水按下列步骤治理和回收利用：A method for the treatment and resource recycling of 1,4-dihydroxyanthraquinone production wastewater, which is to pretreat the production wastewater, that is, for wastewater containing 1,4-dihydroxyanthraquinone less than 10mg/L, pretreatment For direct filtration, for wastewater containing 1,4-dihydroxyanthraquinone higher than 10mg/L, first adjust the pH to 3-4, and then filter to remove 1,4-dihydroxyanthraquinone and suspended matter to ensure The adsorption efficiency of the resin during the treatment process, while improving the purity of recovered phthalic acid, and then the pretreated production wastewater is treated and recycled according to the following steps:
A)将经过预处理的1，4-二羟基蒽醌生产过程中排放的废水在0～60℃的温度和0.5～7BV/h的流量下通过装填有球形颗粒的苯乙烯一二乙烯基苯共聚的大孔吸附树脂并带有加热夹套的吸附塔，使邻苯二甲酸和残存的少量1，4-二羟基蒽醌吸附在大孔吸附树脂上，吸附出水无色透明，CODCr和有机物的含量均在100mg/L以下，可依据其中含酸量的不同和厂家技术、经济等各方面因素的要求回用作生产工段洗涤用水或进行废酸的综合利用或加碱中和后直接排放。A) Pass the pretreated waste water discharged during the production of 1,4-dihydroxyanthraquinone through styrene-divinylbenzene packed with spherical particles at a temperature of 0-60°C and a flow rate of 0.5-7BV/h Copolymerized macroporous adsorption resin and an adsorption tower with a heating jacket, so that phthalic acid and a small amount of residual 1,4-dihydroxyanthraquinone are adsorbed on the macroporous adsorption resin, and the adsorbed water is colorless and transparent, COD Cr and The content of organic matter is below 100mg/L, which can be reused as washing water in the production section or comprehensive utilization of waste acid or directly after neutralization with alkali according to the difference in acid content and the requirements of the manufacturer's technology, economy and other factors. emission.
B)用浓度为0.5～4mol/L的NaOH溶液作为脱附剂，将吸附了邻苯二甲酸和少量1，4-二羟基蒽醌的大孔吸附树脂洗脱再生，洗脱温度为20～95℃，脱附剂流量为0.2～3.0BV/h。B) Use a NaOH solution with a concentration of 0.5-4mol/L as a desorbent to elute and regenerate the macroporous adsorption resin that has adsorbed phthalic acid and a small amount of 1,4-dihydroxyanthraquinone, and the elution temperature is 20-20 95°C, the flow rate of the desorbent is 0.2-3.0BV/h.
C)洗脱下来的高浓度洗脱液部分用浓硫酸调酸至pH＜4～6，过滤，得到邻苯二甲酸晶体，滤液再经过浓缩进一步回收邻苯二甲酸晶体，将两步操作收集到的晶体充分干燥以去除其中水分。浓缩后的残液焚烧处理。洗脱液的低浓度部分用于配制下一批脱附剂循环套用。C) The part of the eluted high-concentration eluent is adjusted to pH<4-6 with concentrated sulfuric acid, filtered to obtain phthalic acid crystals, and the filtrate is concentrated to further recover phthalic acid crystals, and the two-step operation is collected The obtained crystals are sufficiently dried to remove moisture. The concentrated raffinate should be incinerated. The low-concentration part of the eluate is used to prepare the next batch of desorbent for recycling.
上述的苯乙烯-二乙烯基苯共聚大孔吸附树脂可以是国产NDA-404树脂或者CHA-101或X-5或H-103树脂，还可以是美国Rohm-Haas公司生产的AmberliteXAD-2、XAD-4、XAD-7或XAD-8树脂，或者是日本三菱化成公司开发生产的Diaion HP系列大孔吸附树脂，优选的是NDA-404或CHA-101树脂。The above-mentioned styrene-divinylbenzene copolymerized macroporous adsorption resin can be domestic NDA-404 resin or CHA-101 or X-5 or H-103 resin, and can also be AmberliteXAD-2, XAD produced by American Rohm-Haas company -4, XAD-7 or XAD-8 resin, or the Diaion HP series macroporous adsorption resin developed and produced by Japan Mitsubishi Chemical Company, preferably NDA-404 or CHA-101 resin.
上述方法中的脱附剂还可以用甲醇或乙醇代替氢氧化钠水溶液，用甲醇或乙醇做脱附剂时，脱附温度分别为20～50℃和20～70℃，高浓度脱附液经过精馏回收甲醇或乙醇，同时得到邻苯二甲酸和少量1，4-二羟基蒽醌的混合物，于200℃下脱水得到邻苯二甲酸酐，作为原料返回合成工段。洗脱液的低浓度部分用于配制下一批脱附剂循环套用。The desorbing agent in the above method can also use methanol or ethanol instead of sodium hydroxide aqueous solution. When methanol or ethanol is used as the desorbing agent, the desorption temperatures are 20-50°C and 20-70°C respectively, and the high-concentration desorption solution passes through Recover methanol or ethanol by rectification, and at the same time obtain a mixture of phthalic acid and a small amount of 1,4-dihydroxyanthraquinone, dehydrate at 200°C to obtain phthalic anhydride, and return it to the synthesis section as a raw material. The low-concentration part of the eluate is used to prepare the next batch of desorbent for recycling.
本发明1，4-二羟基蒽醌生产废水的治理与资源回收利用方法可以采用双塔串联吸附，单塔脱附的运行方法，即设置I、II、III三个吸附塔，先将I、II塔顺流串联吸附，I塔作为一级吸附塔，II塔作为二级吸附塔，当I塔吸附饱和后，切换成II、III塔顺流串联吸附，II塔作为一级吸附塔，III塔作为二级吸附塔，同时I塔进行逆向脱附，如此循环操作，可以保证整个装置始终连续运行，提高效率。1, the treatment of 4-dihydroxyanthraquinone production waste water of the present invention and resource recycling method can adopt double tower series adsorption, the operation method of single tower desorption, promptly arrange I, II, III three adsorption towers, first I, II, III are arranged Tower II is used for downstream and serial adsorption, tower I is used as the first-level adsorption tower, and tower II is used as the second-level adsorption tower. The tower is used as the second-stage adsorption tower, while the I tower performs reverse desorption. Such a cycle operation can ensure the continuous operation of the whole device and improve the efficiency.
本发明1，4-二羟基蒽醌生产废水的治理与资源回收利用方法可以使CODCr为7000～24000mg/L，含有4700～12000mg/L邻苯二甲酸和7～120mg/L1，4-二羟基蒽醌以及其他极少量有机物的深红色强酸性废水在经过处理后，出水无色透明，CODCr降至100mg/L以下，去除率为99.5％以上，邻苯二甲酸的去除率为99.5％以上，回收率达90％以上，回收晶体纯度为97.9～99.6％，1，4-二羟基蒽醌的去除率为100％。出水可依据其中含酸量的不同和厂家的要求返回到生产工段用作洗涤水或进行废酸的综合利用或直接中和后排放。依据此方法每吨废水中可回收邻苯二甲酸4.23～10.8公斤。The treatment and resource recycling method of 1,4-dihydroxyanthraquinone production waste water of the present invention can make COD Cr 7000～24000mg/L, contain 4700～12000mg/L phthalic acid and 7～120mg/L1,4-Di After treatment, the deep red strong acid wastewater with hydroxyanthraquinone and other very small amount of organic matter will be colorless and transparent, the COD Cr will be reduced to below 100mg/L, the removal rate will be over 99.5%, and the removal rate of phthalic acid will be 99.5% Above, the recovery rate reaches over 90%, the recovered crystal purity is 97.9-99.6%, and the removal rate of 1,4-dihydroxyanthraquinone is 100%. The effluent can be returned to the production section to be used as washing water or comprehensive utilization of waste acid or discharged after direct neutralization according to the difference in acid content and the requirements of the manufacturer. According to this method, 4.23-10.8 kg of phthalic acid can be recovered per ton of waste water.
四、具体实施方式4. Specific implementation
以下通过实施例进一步说明本发明。The present invention is further illustrated by the following examples.
实施例1：将60ml(约45g)NDA-404树脂装入带有保温夹套的玻璃吸附柱(Φ24×320mm)中，室温下(10℃～25℃)让经过过滤的车间排放废水以125ml/h的流量通过树脂床层，废水处理量为600ml/批，废水CODCr浓度为11325.8mg/L，邻苯二甲酸浓度为8174.8mg/L，1，4-二羟基蒽醌浓度为7mg/L，吸附出水无色透明，其中含邻苯二甲酸37.6mg/L，CODCr浓度为64.0mg/L，去除率均高于99.5％；1，4-二羟基蒽醌未检出，去除率为100％。Embodiment 1: 60ml (about 45g) NDA-404 resin is packed in the glass adsorption column (Φ 24 * 320mm) that has insulation jacket, under room temperature (10 ℃～25 ℃) let the workshop discharge waste water through filtering with 125ml The flow rate of /h passes through the resin bed, the wastewater treatment capacity is 600ml/batch, the concentration of COD Cr in wastewater is 11325.8mg/L, the concentration of phthalic acid is 8174.8mg/L, and the concentration of 1,4-dihydroxyanthraquinone is 7mg/L L, the adsorbed water is colorless and transparent, which contains phthalic acid 37.6mg/L, COD Cr concentration is 64.0mg/L, and the removal rate is higher than 99.5%; 1,4-dihydroxyanthraquinone is not detected, the removal rate is 100%.
用120ml 1mol/L的NaOH水溶液在70±5℃的温度下以30ml/h的流量逆流通过树脂床层进行脱附，有机物的脱附率为100％。收集前100ml高浓度脱附液，经过酸析——浓缩两步操作回收邻苯二甲酸晶体，回收量为4.51g，回收率达92.0％。浓缩后的残液焚烧处理。后20ml低浓度脱附液用作下一批脱附剂的配制。Use 120ml 1mol/L NaOH aqueous solution to pass through the resin bed countercurrently at a temperature of 70±5°C at a flow rate of 30ml/h for desorption, and the desorption rate of organic matter is 100%. The first 100ml of high-concentration desorption liquid was collected, and the phthalic acid crystals were recovered through the two-step operation of acid analysis-concentration. The recovery amount was 4.51g, and the recovery rate reached 92.0%. The concentrated raffinate should be incinerated. The last 20ml of low-concentration desorption solution was used for the preparation of the next batch of desorption agent.
实施例2：吸附柱和操作条件同实施例1，但装填Amberlite XAD-4树脂60ml(约45g)，废水中邻苯二甲酸含量从7554.3mg/L降至70.9mg/L，去除率达99.1％，出水无色透明，1，4-二羟基蒽醌未检出。Example 2: The adsorption column and operating conditions are the same as in Example 1, but 60ml (about 45g) of Amberlite XAD-4 resin is filled, and the phthalic acid content in the waste water is reduced from 7554.3mg/L to 70.9mg/L, and the removal rate reaches 99.1 %, the effluent was colorless and transparent, and 1,4-dihydroxyanthraquinone was not detected.
用120ml 2mol/L的NaOH水溶液在90±5℃的温度下以30ml/h的流量逆流通过树脂床层进行脱附，有机物的脱附率为100％。高浓度脱附液回收邻苯二甲酸晶体，回收量为4.15g，回收率达91.6％。低浓度脱附液用作下一批脱附剂的配制。Use 120ml 2mol/L NaOH aqueous solution to pass through the resin bed countercurrently at a temperature of 90±5°C at a flow rate of 30ml/h for desorption, and the desorption rate of organic matter is 100%. The phthalic acid crystals were recovered from the high-concentration desorption liquid, and the recovery amount was 4.15 g, and the recovery rate reached 91.6%. The low-concentration desorption solution is used for the preparation of the next batch of desorption agent.
实施例3：采用三根规格相同的带保温夹套不锈钢吸附柱(Φ250×3500mm)，每柱底部和预部用不锈钢网(50目)覆盖，柱底用粗石英砂(约20L)填充，每柱装填NDA-404树脂90公斤(约120L)，双柱串联吸附，单柱脱附。将CODCr为7000～24000mg/L，邻苯二甲酸浓度为4700～12000mg/L，1，4-二羟基蒽醌浓度为6～120mg/L的生产废水先经过预处理去除其中悬浮物和绝大部分1，4-二羟基蒽醌，再用泵以0.35m3/h的流量自柱顶打入吸附柱，吸附柱采用I、II双柱顺流串联吸附的方式，每批处理量控制在1.5m3左右，出水自II柱底部排至贮槽。处理后的废水无色透明，平均CODCr小于100mg/L，邻苯二甲酸的平均浓度小于50mg/L，1，4-二羟基蒽醌未检出，可直接返回到生产工段用作洗涤水或进行废硫酸的综合利用。Embodiment 3: adopt three stainless steel adsorption columns (Φ 250 * 3500mm) with insulation jacket with the same specification, the bottom of each column and the pre-portion are covered with stainless steel mesh (50 mesh), and the bottom of the column is filled with coarse quartz sand (about 20L). The column is filled with 90 kg (about 120 L) of NDA-404 resin, the double column is connected in series for adsorption, and the single column is desorbed. The production wastewater with COD Cr of 7000-24000mg/L, phthalic acid concentration of 4700-12000mg/L, and 1,4-dihydroxyanthraquinone concentration of 6-120mg/L is pretreated to remove suspended solids and absolute Most of the 1,4-dihydroxyanthraquinone is pumped into the adsorption column from the top of the column at a flow rate of 0.35m 3 /h. The adsorption column adopts the method of I and II double-column parallel flow series adsorption, and the treatment volume of each batch is controlled At about 1.5m 3 , the effluent is discharged from the bottom of the II column to the storage tank. The treated wastewater is colorless and transparent, the average COD Cr is less than 100mg/L, the average concentration of phthalic acid is less than 50mg/L, and 1,4-dihydroxyanthraquinone is not detected, so it can be directly returned to the production section as washing water Or carry out comprehensive utilization of waste sulfuric acid.
每批吸附结束后，I柱进行脱附操作，II、III继续进行吸附操作，此时II柱为首柱。I柱中残液放空后，向夹套中注入热水，使树脂预热至90±5℃，再用0.36m3的8％的NaOH溶液以0.12m3/h的流量自下而上通过树脂床层进行脱附，脱附液进入贮槽，待用。脱附完毕后，用0.25m3的蒸汽冷凝液清洗树脂至中性或弱碱性。After each batch of adsorption is completed, the I column will perform the desorption operation, and the II and III will continue to perform the adsorption operation. At this time, the II column is the first column. After the residual liquid in column I is emptied, inject hot water into the jacket to preheat the resin to 90±5°C, and then use 0.36m 3 of 8% NaOH solution to pass through from bottom to top at a flow rate of 0.12m 3 /h The resin bed is desorbed, and the desorbed liquid enters the storage tank for use. After the desorption is completed, use 0.25m 3 of steam condensate to wash the resin to neutral or weakly alkaline.
III柱与脱附结束后的I柱组成串联吸附，此时III柱为首柱，II柱进行脱附操作。如此循环进行，可保证装置连续运行，提高效率。The III column and the I column after the desorption are completed form a series adsorption. At this time, the III column is the first column, and the II column performs the desorption operation. Such a cycle can ensure the continuous operation of the device and improve the efficiency.
贮槽中的高浓度脱附液先用浓硫酸调至酸性，有晶体析出，过滤收集；过滤后的滤液再进行蒸发浓缩，又有部分晶体析出，过滤收集，烘干后即为高纯度邻苯二甲酸固体。The high-concentration desorption liquid in the storage tank is first adjusted to acidity with concentrated sulfuric acid, and crystals are precipitated, which are collected by filtration; the filtered filtrate is then evaporated and concentrated, and some crystals are precipitated, which is collected by filtration, and it is high-purity ophthalmic acid after drying. Phthalic acid solid.
采用本发明的技术处理1，4-二羟基蒽醌生产废水的方法是有效可行的，在去除废水中有机污染物的同时回收了其中有用的化工原料，同时治理后的出水能套用到生产工艺中作洗涤水，还能进行废酸的综合利用，大大降低了废水的排放量和污染物负荷，对环境保护具有积极的作用。The method of treating 1,4-dihydroxyanthraquinone production wastewater with the technology of the present invention is effective and feasible. While removing organic pollutants in wastewater, useful chemical raw materials are recovered, and the treated effluent can be applied to the production process. Used as washing water, it can also comprehensively utilize waste acid, which greatly reduces the discharge of wastewater and the load of pollutants, and has a positive effect on environmental protection.
实施例4：将实施例1中的吸附树脂改为Amberlite XAD-2、XAD-7、XAD-8或Diaion HP-10、Diaion HP-20、Diaion HP-30树脂以及国产CHA-101、H-103、X-5树脂，除处理废水量有所变化以外，其他结果基本类同。Embodiment 4: Change the adsorption resin in embodiment 1 to Amberlite XAD-2, XAD-7, XAD-8 or Diaion HP-10, Diaion HP-20, Diaion HP-30 resin and domestic CHA-101, H- 103. For X-5 resin, except for the change in the amount of wastewater treated, other results are basically the same.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00112386.6A CN1129556C (en) | 2000-07-10 | 2000-07-10 | Treatment and source recovering method for waste water of 1,4-dihydroxy anthraquinone produetion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00112386.6A CN1129556C (en) | 2000-07-10 | 2000-07-10 | Treatment and source recovering method for waste water of 1,4-dihydroxy anthraquinone produetion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1280102A CN1280102A (en) | 2001-01-17 |
| CN1129556C true CN1129556C (en) | 2003-12-03 |
Family
ID=4582247
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00112386.6A Expired - Fee Related CN1129556C (en) | 2000-07-10 | 2000-07-10 | Treatment and source recovering method for waste water of 1,4-dihydroxy anthraquinone produetion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1129556C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417634C (en) * | 2006-08-25 | 2008-09-10 | 南京大学 | Method for separation and recovery of fumaric acid and phthalic acid in fumaric acid production wastewater |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443417C (en) * | 2004-07-16 | 2008-12-17 | 枝江开元化工有限责任公司 | Recovery method for waste water of 1,4-dihydroxyanthraquinone production |
| CN101519249B (en) * | 2009-04-01 | 2012-06-27 | 东南大学 | Method for treating hydrolyzed waste water and recovering resource in disperse blue production process |
| CN101698699B (en) * | 2009-11-04 | 2013-06-19 | 大连理工大学 | Method for preparing macroporous polymer fixed quinonoid compound |
| CN105693505A (en) * | 2014-11-27 | 2016-06-22 | 江苏华尔化工有限公司 | Treatment method of 1,4-dihydroxyanthraquinone industrial wastewater |
| CN104445781B (en) * | 2014-11-27 | 2016-03-23 | 浙江奇彩环境科技股份有限公司 | A kind of administering method of fused ring compound waste water |
| CN104557504A (en) * | 2014-12-19 | 2015-04-29 | 浙江闰土研究院有限公司 | Clean production technique of 1,4-dihydroxy anthraquinone |
| CN104829505B (en) * | 2015-04-24 | 2016-08-17 | 黎明化工研究设计院有限责任公司 | The separation method of anthraquinone sulfonic acid in the spent acid that a kind of anthraquinone and derivant production process thereof produce |
| CN105367398B (en) * | 2015-11-30 | 2017-08-25 | 盐城市虹艳化工有限公司 | A kind of preparation method of 1,4 dihydroxy anthraquinones without waste discharge |
| CN110194721B (en) * | 2019-06-06 | 2022-05-24 | 浙江工业大学 | Hydroxyphenylglycine centrifugal mother liquor treatment device and method |
| CN111410328A (en) * | 2020-03-30 | 2020-07-14 | 江苏国创新材料研究中心有限公司 | Treatment method of high-concentration organic wastewater |
| CN112028165B (en) * | 2020-08-26 | 2021-03-23 | 广东省肇庆香料厂有限公司 | Method for recovering ethyl maltol from ethyl maltol production wastewater |
| CN115432853B (en) * | 2022-09-02 | 2023-11-21 | 浙江亿得新材料股份有限公司 | Comprehensive utilization method of red acid wastewater |
-
2000
- 2000-07-10 CN CN00112386.6A patent/CN1129556C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100417634C (en) * | 2006-08-25 | 2008-09-10 | 南京大学 | Method for separation and recovery of fumaric acid and phthalic acid in fumaric acid production wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1280102A (en) | 2001-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1129556C (en) | Treatment and source recovering method for waste water of 1,4-dihydroxy anthraquinone produetion | |
| WO2022156623A1 (en) | Comprehensive utilization process of pta oxidation residue | |
| CN101104533A (en) | A kind of treatment method of H-acid production wastewater | |
| CN101244877B (en) | Treatment of waste water in phloroglucinol production process and its recycling method for recovering organic matter | |
| CN100390082C (en) | A kind of treatment and recycling method of dimethyl isophthalate-5-sulfonic acid production wastewater | |
| WO2022156624A1 (en) | Production process for producing plasticizer from pta oxidation residue | |
| CN102234226A (en) | Method for recovering and purifying terephthalic acid in alkali-minimization waste liquor | |
| CN1935704A (en) | Method for treating condensation waste water for producing imidacloprid and resourcized recovering its imidazolidine | |
| CN102527362B (en) | Regeneration method of active carbon for treating decoloring process of analgin | |
| CN108640844B (en) | Method for recovering triethylamine from industrial wastewater | |
| CN1156407C (en) | Treatment and rediaimation of waste water in production of 4,4'-dinitrobistyrene-2,2'-bisulfonic acid | |
| CN1139549C (en) | Method of treating waste water from production of phenylacetic acid and reusing resouce | |
| CN100560512C (en) | A treatment and recycling method of 4,4-diaminostilbene-2,2-disulfonic acid production oxidation wastewater | |
| CN105585212B (en) | A kind of PTA produces waste water method for reusing synthesized | |
| CN104805290A (en) | Method for recovering acetic acid, cobalt and manganese from discharged residues of PTA (purified terephthalic acid) film evaporator | |
| CN116675631B (en) | Cyclic production method of D, L-methionine | |
| CN1246234C (en) | Treatment of waste water in producing isophthalic acid dicarbomethoxy-5-sodium sulphonate and its resource utilization method | |
| CN1803656A (en) | Regeneration treatment method of steel sheet pickling waste liquor | |
| CN106698576B (en) | Treatment method of H acid industrial wastewater | |
| CN100515962C (en) | A kind of method of treating methyl naphthol production waste water and reclaiming methyl naphthol and methyl naphthylamine | |
| CN100352775C (en) | Method for treating sewage generated by preparing methyl salicylate and resource recorery by composite technology | |
| CN100415654C (en) | Method for purification and resource recycling of H acid production wastewater | |
| CN1364733A (en) | Waste water treating and resource recovering method for 1,2-diazo-oxy-naphthalene-4-sulfonic acid production | |
| CN100361724C (en) | A kind of treatment method of N-acetoacetylaniline production wastewater | |
| CN1280206C (en) | Method for treatng wastewater of producing reactive dyes in class of bromamine acid, and for reclaiming resources |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| 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 |