CN108484384A - The technique for preparing fumaric acid using maleic acid waste water - Google Patents
The technique for preparing fumaric acid using maleic acid waste water Download PDFInfo
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- CN108484384A CN108484384A CN201810140643.4A CN201810140643A CN108484384A CN 108484384 A CN108484384 A CN 108484384A CN 201810140643 A CN201810140643 A CN 201810140643A CN 108484384 A CN108484384 A CN 108484384A
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- fumaric acid
- waste water
- maleic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/09—Geometrical isomers
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- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of techniques preparing fumaric acid using maleic acid waste water, include the following steps：（1）Catalysis reaction, it is 100 maleic acid waste water to take mass fraction, and the thiourea catalyst that mass fraction is 5.5 ~ 6 parts is added, is stirred to react 12h at normal temperatures, obtains fumaric acid crude product；（2）Washing, takes fumaric acid crude product, is washed with distilled water, then add distilled water, is heated to 95 ~ 100 DEG C of dissolvings, adds the activated carbon decolorizing after activation, obtain pure fumaric acid；（3）Purifying reaction, takes a certain amount of pure fumaric acid, is first washed with distilled water, and the activated carbon after activation is then added, and decolourize back flow reaction 2h, obtains food-grade fumaric acid.Maleic acid in industrial acidic wastewater is transformed into fumaric acid by the present invention using isomerization reaction, is turned waste into wealth, and the economic benefit of company is increased.
Description
Technical field
The present invention relates to wastewater utilization technical fields, and fumaric acid is prepared using maleic acid waste water more particularly to a kind of
Technique.
Background technology
Chemical plant, which is used as, uses water rich and influential family, and year, fresh water consumption was generally hundreds of ten thousand steres, and the recycling rate of waterused of water is low, together
When hundreds of ten thousand stere of externally discharged waste water, not only waste great lot of water resources, also result in environmental pollution, and the shortage of water resource is right
The production of these industrial waters rich and influential family threatens.To keep the sustainable development of enterprise and reducing the waste of water resource, reduce
Production cost improves Business Economic Benefit and social benefit.Advanced treating need to be carried out to wastewater from chemical industry（Tertiary treatment）, as following
Reusing sewage is realized in the moisturizing of ring water or the moisturizing of power desalted water.
Currently, industrially mainly passing through the isomerate process of maleic acid, furfural oxidizing process, maleic acid enzymatic isomerate process, paraffin
The methods of fermentation method and biomass material fermentation method prepare fumaric acid.All it is to select petroleum-based products in these production methods
For raw material.But the positive increasingly depleted of oil, in order to make full use of petroleum-based products and implement environmentally protective policy, fumaric acid (anti-fourth
Enedioic acid) isomery production technology is to be less than the solubility of maleic acid in water using the solubility of fumaric acid in water this is special
Property, it is fumaric acid by Isomerization of Maleic Acid, to reach the separation with water.
Maleic acid be industrial production naphthalene and o xylene oxidation generate be widely present in the waste material of phthalic anhydride it is a kind of to environment
Harmful pollutant.Using ortho-xylene as raw material, phthalic anhydride is produced using fixed bed catalytic oxidation method technology, it has also become phthalic anhydride
The mainstream of industry.In phthalic anhydride technique, ortho-xylene is heated to mix vaporization with hot-air, under the effect of the catalyst, solid
Phthalic anhydride is generated in fixed bed reactor, while generating maleic anhydride, after supercooling, switching condensation, washing, maleic two
Anhydride conversion is maleic acid (abbreviation maleic acid), and mass fraction is 25% or so.These industrial wastes mainly use at present
The processing mode of direct emission, thus can cause environmental pollution.Therefore, maleic acid is extracted from industrial waste, and by its turn
Chemical conversion fumaric acid has important practical significance.
Invention content
The invention mainly solves the technical problem of providing a kind of techniques preparing fumaric acid using maleic acid waste water, utilize
Maleic acid in industrial acidic wastewater is transformed into fumaric acid by isomerization reaction, is turned waste into wealth, and the economic benefit of company is increased.
In order to solve the above technical problems, one aspect of the present invention is：
A kind of technique being prepared fumaric acid using maleic acid waste water is provided, is included the following steps：
（1）Catalysis reaction, it is 100 maleic acid waste water to take mass fraction, and the thiocarbamide that mass fraction is 5.5 ~ 6 parts is added and is catalyzed
Agent is stirred to react 12h at normal temperatures, obtains fumaric acid crude product；
（2）Washing, takes fumaric acid crude product, is washed with distilled water, then add distilled water, is heated to 95 ~ 100 DEG C of dissolvings, then
Activated carbon decolorizing is added, obtains pure fumaric acid；
（3）Purifying reaction, takes a certain amount of pure fumaric acid, is first washed with distilled water, after the activation after activation is then added
Activated carbon, decolourize back flow reaction 2h, obtains food-grade fumaric acid.
In a preferred embodiment of the present invention, the catalysis reaction carries out in isomerization reaction kettle, the isomerization reaction
The volume of kettle is 10 cubic metres.
In a preferred embodiment of the present invention, in purifying reaction, after fumaric acid crude product is washed with distilled water,
It is sent into centrifuge separation, the fumaric acid crude product after then washing adds distillation water process.
In a preferred embodiment of the present invention, the washes generated later is washed with distilled water in fumaric acid crude product,
Continue to put into production link as recirculated cooling water.
In a preferred embodiment of the present invention, in step（3）In purifying reaction, after back flow reaction of decolourizing, material is sent
Enter continuous crystallisation machine to be crystallized, temperature is controlled at 25 DEG C or less.
In a preferred embodiment of the present invention, the fumaric acid of crystallization is fed again into centrifuge and is centrifuged, rear low temperature is dry
It is dry to obtain the fumaric acid of food-grade.
In a preferred embodiment of the present invention, in the step（2）In, the quality of the activated carbon after the activation of addition is
The 14% of fumaric acid crude product quality.
In a preferred embodiment of the present invention, in step（3）The quality of activated carbon after the activation of middle addition is pure
Fumaric acid quality 14%.
The beneficial effects of the invention are as follows：The present invention prepares the technique of fumaric acid using maleic acid waste water, using meeting to environment
The waste water that the waste water or needs polluted could discharge after processing extracts the fumaric acid of food-grade, not only drops as raw material
The low pollution to environment, and data is effectively utilized, produce certain economic value；And the technique step in the present invention
Rapid simple, condition controllability amount is good, and the yield of food-grade fumaric acid product can reach 82% or more.
Specific implementation mode
The preferred embodiments of the present invention will be described in detail below so that advantages and features of the invention can be easier to by
It will be appreciated by those skilled in the art that so as to make a clearer definition of the protection scope of the present invention.
A kind of technique preparing fumaric acid using maleic acid waste water, reaction equation are：
,
Specifically include following step：
（1）Catalysis reaction, it is 100 maleic acid waste water to take mass fraction, and the thiocarbamide that mass fraction is 5.5 ~ 6 parts is added and is catalyzed
Agent is stirred to react 12h at normal temperatures, obtains fumaric acid crude product；Catalysis reaction carries out in isomerization reaction kettle, and the isomery is anti-
It is cylindrical reaction kettle to answer kettle, and volume is 10 ~ 12 cubic metres, and 10 cubic metres are used in the present embodiment；
（2）Washing, takes fumaric acid crude product, is washed with distilled water, then add distilled water, is heated to 95 ~ 100 DEG C of dissolvings, then
Activated carbon decolorizing is added, obtains pure fumaric acid；In the washing step, after fumaric acid crude product is washed with distilled water,
It is sent into centrifuge separation, the fumaric acid crude product after then washing adds distillation water process；It is steamed in fumaric acid crude product
Distilled water washs the washes generated later, continues to put into production link as recirculated cooling water；
（3）Purifying reaction, takes a certain amount of pure fumaric acid, is first washed with distilled water, and the activated carbon after activation is then added, takes off
Color back flow reaction 2h, obtains food-grade fumaric acid；In purifying reaction, after back flow reaction of decolourizing, material is sent into continuous knot
Brilliant machine is crystallized, and temperature is controlled at 25 DEG C or less.The fumaric acid of crystallization is fed again into centrifuge and is centrifuged, rear low temperature drying
Obtain the fumaric acid of food-grade.
The fumaric acid that above-mentioned processing step obtains carries out the measurement of content according to the following steps：
The fumaric acid sample of 1.0g food-grades is weighed, weight is accurate to 0.0002g, is put into 250mL conical flasks, adds 100mL
Water dissolves by heating, and after cooling plus 3 drip instructions phenolphthalein solutions, are titrated to blush with standard solution of sodium hydroxide, 30s is kept not take off
Color is terminal.
While measuring, the step identical as measurement is pressed, is done using the reagent solution of identical quantity to being not added with sample
Blank test.
Standard Volumetric Solutions for Sodium Hydroxide：C (NaOH)=0.5mol/L.
Instructions phenolphthalein solution：10g/L.
2）The measurement of moisture：
Constant Temp. Oven is adjusted to（105±2）DEG C, measuring cup is then placed in drying in Constant Temp. Oven, is taken
It is cooling in drier after going out that [cooling time is generally（20~40）Min has to cooling time of repetitive operation identical], claim
Amount, is accurate to 0.1mg, is operated repeatedly to constant weight.
With the measuring cup of constant weight, about 1g samples are weighed.Sample surface gently flattens, and is put into and is adjusted to（105±2）℃
Constant Temp. Oven in（Measuring cup should be placed on around thermometer mercury ball）.Measuring cup lid be slightly staggered or remove with
Sample is dry simultaneously.
It is dry（2~4）After h, measuring cup and lid are moved to rapidly cooling in drier.Lid is covered after cooling, is weighed,
It is accurate to 0.1mg, repetitive operation to constant weight, it is about 1h to repeat drying time.
In terms of mass fraction w, numerical value is indicated moisture with %, is pressed examination and is calculated：
In formula：
m0--- the numerical value of the quality of measuring cup, unit are gram（g）；
m1--- the numerical value of measuring cup and dry preceding sample mass, unit are gram（g）；
m2--- the numerical value of sample mass after measuring cup and drying, unit are gram（g）.
It is measurement result to take the arithmetic mean of instantaneous value of parallel determinations, and the absolute difference of parallel determinations meets production twice
Product provide.
Step in fumaric acid preparation process（3）In purifying reaction, at different temperatures, fumaric acid crude product is completely molten
Water consumption needed for solution is as shown in the table：
The raising of the solubility with temperature of fumaric acid and increase, therefore the purifying of fumaric acid crude product reaction in, using 95 ~ 100
DEG C distilled water dissolved, need water to be used less.
In washing process, 100 DEG C of dissolving fumaric acid crude products are heated to using with 150ml distilled water, after activation is added
Activated carbon, be stirred at reflux reaction 2h.It filters, one night of filtrate cooling and standings.The solid that filtrate is precipitated is filtered, is dried,
It weighs to obtain solid.
As can be seen from the above table, refine after product, that is, pure grade fumaric acid product, yield with activated carbon dosage increase
And improve, but activated carbon dosage can excessively cause yield to decline instead, the impurity that activated carbon can not only be in adsorption production, when it
Amount it is bigger when, product can be tightly held by activated carbon, to reduce yield.
After distilling water washing crude product, content of the fumaric acid in crude product, the quality lost each time after washing are improved
It is 1/6=16.7%.
In purifying is reacted, 6g crude products are taken, 30ml is added to distill water washing 30min, are filtered, drying, with 150ml distilled water
It is heated to 100 DEG C and dissolves this crude product, add the activated carbon after activation, be stirred at reflux reaction 2h.Filtrate evaporates 10% water, filter
One night of liquid cooling and standings.The solid that filtrate is precipitated is filtered, is dried, solid of weighing to obtain.
In addition, equally taking 6g crude products in purifying is reacted, 30ml is added to distill water washing 30min, filters, drying, use
150ml distilled water is heated to 100 DEG C and dissolves this crude product, adds the activated carbon after activation, is stirred at reflux reaction 2h.Filtrate evaporates
20% water, one night of filtrate cooling and standings.The solid that filtrate is precipitated is filtered, is dried, solid of weighing to obtain.
It can be obtained by the data in above three table, be continuously increased with the dosage of activated carbon, product yield is first
It is reduced after raising.Activated carbon dosage is at 14%, product yield highest, up to 80% or more.
Therefore in present invention process, water consumption is lower, and under identical activated carbon dosage, product yield is higher.Water consumption is
It has been saturation state when 120ml, therefore has been not suitable for reducing water consumption again.Finally we obtain, when water consumption is 120ml, production
Product yield may be up to 82.0%.
In the purifying process of fumaric acid, the impurity in crude product is adsorbed by the way that activated carbon is added, activated carbon needs to activate,
Adsorption effect can be only achieved most preferably, before decoloration, first be washed with water, and then plus activated carbon back flow reaction is decolourized, and finally obtains food
Grade product fumaric acid.In order to further increase product yield, the filtrate after back flow reaction is evaporated into a part of water, in order to
More products are precipitated.
The present invention prepares the technique of fumaric acid using maleic acid waste water, using the waste water or needs that can cause environmental pollution
The waste water that could be discharged after processing extracts the fumaric acid of food-grade as raw material, not only reduces the pollution to environment, and
Data is effectively utilized, certain economic value is produced；And the processing step in the present invention is simple, condition controllability amount
Good, the yield of food-grade fumaric acid product can reach 82% or more.
Example the above is only the implementation of the present invention is not intended to limit the scope of the invention, every to utilize this hair
Equivalent structure or equivalent flow shift made by bright description is applied directly or indirectly in other relevant technology necks
Domain is included within the scope of the present invention.
Claims (8)
1. a kind of technique preparing fumaric acid using maleic acid waste water, which is characterized in that include the following steps：
（1）Catalysis reaction, it is 100 maleic acid waste water to take mass fraction, and the thiocarbamide that mass fraction is 5.5 ~ 6 parts is added and is catalyzed
Agent is stirred to react 12h at normal temperatures, obtains fumaric acid crude product；
（2）Washing, takes fumaric acid crude product, is washed with distilled water, then add distilled water, is heated to 95 ~ 100 DEG C of dissolvings, then
The activated carbon decolorizing after activation is added, obtains pure fumaric acid；
（3）Purifying reaction, takes a certain amount of pure fumaric acid, is first washed with distilled water, and the activated carbon after activation is then added, takes off
Color back flow reaction 2h, obtains food-grade fumaric acid.
2. the technique according to claim 1 for preparing fumaric acid using maleic acid waste water, which is characterized in that the catalysis is anti-
It should be carried out in isomerization reaction kettle, the volume of the isomerization reaction kettle is 10 cubic metres.
3. the technique according to claim 1 for preparing fumaric acid using maleic acid waste water, which is characterized in that in the purifying
In reaction, after fumaric acid crude product is washed with distilled water, it is sent into centrifuge separation, the fumaric acid crude product after then washing
Add distillation water process.
4. the technique according to claim 3 for preparing fumaric acid using maleic acid waste water, which is characterized in that thick in fumaric acid
Product are washed with distilled water the washes generated later, continue to put into production link as recirculated cooling water.
5. the technique according to claim 1 for preparing fumaric acid using maleic acid waste water, which is characterized in that in step（3）
In purifying reaction, after back flow reaction of decolourizing, material feeding continuous crystallisation machine is crystallized, temperature is controlled at 25 DEG C or less.
6. the technique according to claim 5 for preparing fumaric acid using maleic acid waste water, which is characterized in that by the richness of crystallization
Horse acid, which is fed again into centrifuge, to be centrifuged, and rear low temperature drying obtains the fumaric acid of food-grade.
7. the technique according to claim 1 for preparing fumaric acid using maleic acid waste water, which is characterized in that in the step
（2）In, the quality of the activated carbon after the activation of addition is the 14% of fumaric acid crude product quality.
8. the technique according to claim 1 for preparing fumaric acid using maleic acid waste water, which is characterized in that in step（3）
The quality of activated carbon after the activation of middle addition is the 14% of the quality of pure fumaric acid.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810140643.4A CN108484384A (en) | 2018-02-11 | 2018-02-11 | The technique for preparing fumaric acid using maleic acid waste water |
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| CN201810140643.4A CN108484384A (en) | 2018-02-11 | 2018-02-11 | The technique for preparing fumaric acid using maleic acid waste water |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210112914A (en) | 2020-03-06 | 2021-09-15 | 숙명여자대학교산학협력단 | Variable structure metal-organic framework and manufacturing method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204772A (en) * | 2012-01-17 | 2013-07-17 | 新疆金源石油化工有限公司 | Method for producing fumaric acid by maleic anhydride waste water |
| CN103601637A (en) * | 2013-11-22 | 2014-02-26 | 昆山美淼环保科技有限公司 | Treatment method for recovering fumaric acid from phthalic anhydride wastewater |
| 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 |
| CN105439844A (en) * | 2014-08-27 | 2016-03-30 | 常茂生物化学工程股份有限公司 | Method for coproducing maleic acid and fumaric acid from maleic anhydride acid water |
-
2018
- 2018-02-11 CN CN201810140643.4A patent/CN108484384A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103204772A (en) * | 2012-01-17 | 2013-07-17 | 新疆金源石油化工有限公司 | Method for producing fumaric acid by maleic anhydride waste water |
| CN103601637A (en) * | 2013-11-22 | 2014-02-26 | 昆山美淼环保科技有限公司 | Treatment method for recovering fumaric acid from phthalic anhydride wastewater |
| 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 |
| CN105439844A (en) * | 2014-08-27 | 2016-03-30 | 常茂生物化学工程股份有限公司 | Method for coproducing maleic acid and fumaric acid from maleic anhydride acid water |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20210112914A (en) | 2020-03-06 | 2021-09-15 | 숙명여자대학교산학협력단 | Variable structure metal-organic framework and manufacturing method thereof |
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