CN103204772A - Method for producing fumaric acid by maleic anhydride waste water - Google Patents
Method for producing fumaric acid by maleic anhydride waste water Download PDFInfo
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- CN103204772A CN103204772A CN 201210013608 CN201210013608A CN103204772A CN 103204772 A CN103204772 A CN 103204772A CN 201210013608 CN201210013608 CN 201210013608 CN 201210013608 A CN201210013608 A CN 201210013608A CN 103204772 A CN103204772 A CN 103204772A
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Abstract
The invention relates to a method for producing fumaric acid by maleic anhydride waste water. The method comprises an isomerization reaction process of the maleic anhydride waste water, a centrifugal separation process of fumaric acid head products, a dissolution and decoloration process of the fumaric acid, a filtration process, a crystallization and re-crystallization process of the fumaric acid, a centrifugation process and a drying and packaging process of the fumaric acid. Specifically, the method comprises the steps of adding a catalyst to the maleic anhydride waste water to carry out the isomerization reaction, adding activated carbon to carry out dissolution and decoloration, filtration and crystallization and re-crystallization after the centrifugal separation, then centrifuging, drying and packaging to obtain the fumaric acid. With the method, the fumaric acid in waste acid water generated in production process by using the maleic anhydride can be fully recovered and industrial grade fumaric acid products can be made, so that discharging amount of waste can be reduced maximally, valuable fumaric acid resource can be recovered, and reutilization of the resource is realized. The preparation method is simple and controllable in process, relatively low in cost and has significant social and economic benefits.
Description
Technical field
The present invention relates to the acyclic or isocyclic compound technology of International Classification of Patents CO7C, especially produce the method for fumaric acid with waste water of cis-anhydride.
Background technology
The industrial production of China Maleic Anhydrite starts from the 1950's, but owing to reactor design with reasons such as manufacture level is limited and catalyst performance is relatively poor, it is high, seriously polluted to consume, production equipment small scales, develops very slow.After the eighties in 20th century, ton cis-butenedioic anhydride production equipment was used, each economic targets such as quality product, raw materials consumption were improved.The technology of the present benzene of employing usually fixed bed oxidation style production cis-butenedioic anhydride is comparative maturity, technology and AlusllisldUCB method are roughly the same, but dimethylbenzene azeotropic dehydration technology is adopted in aftertreatment, and usually in benzene oxidation method for preparing cis-butenedioic anhydride fixed bed device, especially payes attention to Application of Catalyst.
In the known technology, produce in the cis-butenedioic anhydride process in the normal butane method, the capital produces some waste liquids, waste liquid mainly comes self-stip rectifying tower still water, calculate to produce 40000 tons of cis-butenedioic anhydride scales per year, produce in year about more than 14000 ton of waste liquid, it mainly consists of toxilic acid and accounts for 11-12%, fumaric acid accounts for 18.6%, other materials account for 5.07%, all the other are water, because toxilic acid and fumaric acid are isomerss, it can transform under certain conditions mutually, and fumaric acid solubleness in water is less under the normal temperature, be 0.63 as 25 ℃ of solubleness, so utilize this characteristic that waste water is lowered the temperature, with have fumaric acid crystallization in the waste water separate out with the toxilic acid aqueous solution separately, do not see open and improve technology accordingly.
In the known technology, adopt two-stage SBR technology that cis-butenedioic anhydride and waste water for fumaric acid production are handled, having investigated sludge concentration, reaction times to the Changing Pattern of pH in the influence for the treatment of effect and the reaction process. the result shows, MLSS is 5.9g/L than MLSS is that the treatment effect of 11.2g/L is good.CODCr is 6300mg/L when water inlet, BOD5 is 4715mg/L, NH3-N is 369mg/L, test is in water-filling 1h, precipitation 2h, idle 3h, the non-aeration of limiting the quantity of, one-level SBR (MLSS is 5.9g/L) reaction times 10h, secondary SBR (MLSS is 4.1g/L) reaction 18h condition following time, CODCr is that 648mg/L, clearance are 89.7% in the water outlet, BOD5 is that 85mg/L, clearance are 98.2%, NH3-N is that to be 94.6%.pH raise with the reduction of CODCr for 20mg/L, clearance, when the reduction amplitude of CODCr eased up, the rising amplitude of pH was also along with easing up.
Relevant improvement technology is also rarely open.
As, the by product of number of patent application 200810045844 usefulness cis-butenedioic anhydride productions prepares the method for BDO or succinate, wherein by product comprises at least a in waste water, waste residue, the maleic anhydride residue, the preparation method comprises key steps such as esterification, distillation, reduction, can obtain BDO or succinate product etc.
The production method of number of patent application 201010114212.4 fumaric acid, particularly a kind of is the production method of the fumaric acid of raw material with benzene anhydride oxidized reaction end gas absorption sour water.This method may further comprise the steps: a. will add the decolouring still from the maleic acid aqueous solution of phthalic anhydride production equipment, add activated carbon and carry out adsorption bleaching; B. the previous step filtrate filtered is changed in the reactor, add phosphoric acid and diformazan chalcogen (selenium/tellurium) composite catalyst and carry out isomerization reaction; The weight ratio of diformazan chalcogen selenium acid amides and diformazan chalcogen tellurium acid amides is 1: 0.1～0.5 in diformazan chalcogen (selenium/tellurium) the acid amides composite catalyst; C. in crystallization kettle, the aqueous acid that changes into fumaric acid is carried out crystallisation by cooling under whipped state, be cooled to the sour water temperature and reach 30 ℃; Discharging while stirring is the fumaric acid finished product to solid-liquid separating equipment after the gained solid matter drying equipment drying.
Summary of the invention
The purpose of this invention is to provide a kind of method of producing fumaric acid with waste water of cis-anhydride.
Goal of the invention of the present invention realizes by following technical measures: comprise toxilic acid isomerization reaction operation, fumaric acid head product centrifugal separation process, fumaric acid dissolving decolorization filtering operation, fumaric acid recrystallization, rotary process and fumaric acid drying and packaging process; Comprise that specifically the toxilic acid aqueous solution adds catalyzer and carries out isomerization reaction, pass through centrifugation again after, add gac and dissolve decolouring, filtration and crystallization, recrystallization, make through centrifugal, dry packing again.
The invention has the beneficial effects as follows: can fully recycle the fumaric acid resource of the preciousness in the waste acid water in the cis-anhydride production process, realize the recycling of resource, solve the production way of escape problem of maleic anhydride unit; The protection environment has been made important exemplary role; And this preparation method's technological process simple controllable, cost is lower, and society and economic benefit are good.
Description of drawings
Fig. 1 is preparation technology's synoptic diagram of the present invention
Embodiment
Comprise toxilic acid isomerization reaction operation, fumaric acid head product centrifugal separation process, fumaric acid dissolving bleaching process in the technology of the present invention, filter operation, fumaric acid recrystallization operation, rotary process and fumaric acid dry packing operation.Comprise that specifically waste water of cis-anhydride adds catalyzer and carries out isomerization reaction, through after the centrifugation, add gac and dissolve decolouring, filtration and crystallization, recrystallization, make through centrifugal, drying again.Can fully recycle the fumaric acid in the waste acid water in the cis-anhydride production process, and be refined into technical grade fumaric acid finished product.
Wherein, toxilic acid isomerization reaction operation comprises: the toxilic acid aqueous solution after will cooling is with being pumped in the isomerization reaction still, the isomerization still is selected 12 cubes of reactors for use, the catalyzer that adds toxilic acid content 3-3.5%, be warmed up to 85 ℃-90 ℃, the reaction times was controlled at 2 hours, then decrease temperature crystalline, temperature control obtains the fumaric acid head product below 25 ℃.
Toxilic acid isomerization reaction principle is:
Wherein, fumaric acid head product centrifugal separation process comprises: the fumaric acid crystallisate of decrease temperature crystalline is carried out centrifugation with whizzer, separate mother liquor and send water treatment to carry out art breading, the fumaric acid solid send the decolouring of decolouring still.
Wherein, fumaric acid dissolving decolorization filtering operation comprises: the fumaric acid waste residue that fumaric acid head product and the waste water naturally cooling of centrifugation obtained joins branch and answers in the still, the an amount of water of dissolution characteristics adding according to fumaric acid makes its dissolving, the gac that adds fumaric acid content 5-10% simultaneously, stirring also is warming up to more than 95 ℃ stirring reaction 2 hours.Getting to flame filter press with spiral pump then filters.
Wherein, fumaric acid recrystallization, rotary process comprise: the fumaric acid solution of decolorization filtering is delivered to the continuous crystallisation machine carry out crystallization, and control cooling extent≤5 ℃, stirring velocity 5-6 rice/minute, crystallization, temperature is controlled below 25 ℃.The fumaric acid suspension of decrease temperature crystalline is carried out centrifugation with whizzer, separate mother liquor and carry out recycling, the fumaric acid solid is delivered to vibrated fluidized bed through the spiral feeder and is carried out drying.
Wherein, the fumaric acid drying process: drying plant adopts vibrated fluidized bed, and per hour treatment capacity is 500-600Kg, and drying temperature is controlled at 130～150 ℃, and the control index mainly is moisture content, water content≤0.5% of control material, and it is qualified to be.
At last, as Industrial products, dry qualified fumaric acid is delivered to finished product bin, is carried out quantitative package by automatic packing machine through the spiral feeder, the wrapping machine treatment capacity be 300 bags/hour, every bag 25Kg.
The fumaric acid product that the present invention produces, appearance white crystalloid powder, in fumaric acid purity 〉=98.5%, moisture content≤0.5%, fusing point 286-302 ℃, colourity≤60Hazen in ash≤0.1%, 5% ethanol.
One ton of fumaric acid norm quota of consumption of every production, in the waste water of cis-anhydride toxilic acid by 11%, the catalyzer dosage press toxilic acid 3%, transformation efficiency presses 95%, the fumaric acid yield is by 80%.
Mature production technology of the present invention, belong to the ecological environment-friendly type material, be raw material to produce waste water of cis-anhydride, by operations such as isoversion, centrifugal, washing, dissolving, decolouring, crystallization, separation, drying, packings, produce technical grade fumaric acid purity 〉=99%, 295 ℃ of fusing points, yield 〉=80%.
Main raw material among the present invention in the fumaric acid production process is for producing waste water of cis-anhydride, and the crystal water that produces in the gac of the principal pollutant refining decolorization inactivation that is fumaric acid and the fumaric acid crystallisation process, the gac of inactivation produces 470 kilograms every day, crystal water produces 70 tons every day, these are all to obtain harmless treatment, gac as inactivation send cis-butenedioic anhydride roasting kiln incinerating method to handle, simultaneously all right recovered energy; And a crystal water part can be carried out recycling, and another small portion adopts reversible complexometric extraction and catalyzed oxidation technology or utilizes the rich steam raising of cis-butenedioic anhydride to handle.
Claims (7)
1. produce the method for fumaric acid with waste water of cis-anhydride, it is characterized in that waste water of cis-anhydride isomerization reaction operation, fumaric acid head product centrifugal separation process, fumaric acid dissolving bleaching process, filter operation, fumaric acid crystallization, recrystallization operation, rotary process and fumaric acid drying and packaging process, specifically comprise, the Malaysia sour water adds catalyzer and carries out isomerization reaction, after passing through centrifugation again, add gac and dissolve decolouring, filtration and crystallization, recrystallization, make through centrifugal, dry packing again.
2. method of producing fumaric acid with waste water of cis-anhydride as claimed in claim 1, it is characterized in that, waste water of cis-anhydride isomerization reaction operation comprises: the waste water of cis-anhydride after will cooling is with being pumped in the isomerization reaction still, the isomerization still is selected 12 cubes of reactors for use, adds the catalyzer of toxilic acid content 3-3.5%, is warmed up to 85 ℃-90 ℃, reaction times, control was at 2 hours, decrease temperature crystalline then, temperature is controlled below 25 ℃, obtains the fumaric acid head product.
3. method of producing fumaric acid with waste water of cis-anhydride as claimed in claim 1, it is characterized in that, fumaric acid head product centrifugal separation process comprises: the fumaric acid crystallisate of decrease temperature crystalline is carried out centrifugation with whizzer, separate mother liquor and send water treatment to carry out art breading, the fumaric acid solid send the decolouring of decolouring still.
4. method of producing fumaric acid with waste water of cis-anhydride as claimed in claim 1, it is characterized in that, fumaric acid dissolving decolorization filtering operation comprises: with the fumaric acid head product of centrifugation and waste water is cold naturally that the fumaric acid head product that obtains is joined in the reactor, add after an amount of water treats that it dissolves fully according to the dissolution characteristics of fumaric acid, the gac that adds fumaric acid content 5-10% simultaneously, stir and be warming up to more than 95 ℃, stirring reaction 2 hours is got to flame filter press with spiral pump then and is filtered.
5. method of producing fumaric acid with waste water of cis-anhydride as claimed in claim 1, it is characterized in that, fumaric acid crystallization, recrystallization, rotary process comprise: the fumaric acid solution of decolorization filtering is delivered to the continuous crystallisation machine carry out crystallization, control cooling extent≤5 ℃, stirring velocity 5-6 rev/min, Tc control is below 25 ℃, the fumaric acid suspension of decrease temperature crystalline is carried out centrifugation with whizzer, separate mother liquor and carry out recycling, the fumaric acid solid is delivered to vibrated fluidized bed through the spiral feeder and is carried out drying.
6. method of producing fumaric acid with waste water of cis-anhydride as claimed in claim 1, it is characterized in that, the fumaric acid drying process: drying plant adopts vibrated fluidized bed, per hour treatment capacity is 500-600Kg, drying temperature control is at 130～150 ℃, the control index mainly is moisture content, water content≤0.5% of control material, and it is qualified to be.
7. method of producing fumaric acid with waste water of cis-anhydride as claimed in claim 1 is characterized in that, makes product appearance white crystals sprills, in fumaric acid purity 〉=98.5%, moisture content≤0.5%, fusing point 286-302 ℃, colourity≤60Hazen in ash≤0.1%, 5% ethanol.
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| CN 201210013608 CN103204772A (en) | 2012-01-17 | 2012-01-17 | Method for producing fumaric acid by maleic anhydride waste water |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016852A (en) * | 2014-02-17 | 2014-09-03 | 华东理工大学 | Novel production process of fumaric acid with low color number and high purity |
| CN104262136A (en) * | 2014-08-28 | 2015-01-07 | 铜陵化工集团有机化工有限责任公司 | Method for recycling fumaric acid from phthalic anhydride production wastewater |
| CN108484384A (en) * | 2018-02-11 | 2018-09-04 | 常熟联邦化工股份有限公司 | The technique for preparing fumaric acid using maleic acid waste water |
| KR20190094031A (en) * | 2018-02-02 | 2019-08-12 | 주식회사 엘지화학 | Method for preparing imide compounds |
| CN112588220A (en) * | 2020-12-16 | 2021-04-02 | 罗兵甲 | Device for preparing fumaric acid from maleic anhydride in industrial production |
| CN112724009A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Method for producing fumaric acid from maleic anhydride wastewater |
| CN116239333A (en) * | 2023-05-11 | 2023-06-09 | 湖南高翔新材料有限公司 | Production process of antifreeze concrete additive |
-
2012
- 2012-01-17 CN CN 201210013608 patent/CN103204772A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016852A (en) * | 2014-02-17 | 2014-09-03 | 华东理工大学 | Novel production process of fumaric acid with low color number and high purity |
| CN104262136A (en) * | 2014-08-28 | 2015-01-07 | 铜陵化工集团有机化工有限责任公司 | Method for recycling fumaric acid from phthalic anhydride production wastewater |
| CN104262136B (en) * | 2014-08-28 | 2016-07-06 | 铜陵化工集团有机化工有限责任公司 | Phthalic anhydride produces the method for waste water reclamation fumaric acid |
| KR20190094031A (en) * | 2018-02-02 | 2019-08-12 | 주식회사 엘지화학 | Method for preparing imide compounds |
| KR102275849B1 (en) | 2018-02-02 | 2021-07-12 | 주식회사 엘지화학 | Method for preparing imide compounds |
| CN108484384A (en) * | 2018-02-11 | 2018-09-04 | 常熟联邦化工股份有限公司 | The technique for preparing fumaric acid using maleic acid waste water |
| CN112724009A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Method for producing fumaric acid from maleic anhydride wastewater |
| CN112724009B (en) * | 2019-10-14 | 2022-11-25 | 中国石油化工股份有限公司 | Method for producing fumaric acid from maleic anhydride wastewater |
| CN112588220A (en) * | 2020-12-16 | 2021-04-02 | 罗兵甲 | Device for preparing fumaric acid from maleic anhydride in industrial production |
| CN116239333A (en) * | 2023-05-11 | 2023-06-09 | 湖南高翔新材料有限公司 | Production process of antifreeze concrete additive |
| CN116239333B (en) * | 2023-05-11 | 2023-07-07 | 湖南高翔新材料有限公司 | Production process of antifreeze concrete additive |
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Application publication date: 20130717 |