CN106366058B - A kind of method of comprehensive utilization of inclined anhydride heavy constituent by-product - Google Patents
A kind of method of comprehensive utilization of inclined anhydride heavy constituent by-product Download PDFInfo
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- CN106366058B CN106366058B CN201610735819.1A CN201610735819A CN106366058B CN 106366058 B CN106366058 B CN 106366058B CN 201610735819 A CN201610735819 A CN 201610735819A CN 106366058 B CN106366058 B CN 106366058B
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Abstract
The present invention proposes the integrated conduct method of black slag generated in inclined acid anhydride production, including：(1) in the dissolved solution ethanol water of black slag, 1 3h of dissolving stirring；(2) dissolved product is put into quiescent settling 3 12 hours in a settling tank, after solid-liquid significantly layering, upper solution suction centrifuge is centrifuged with pump, obtains filtrate；(3) filtrate is distilled, first steams water and ethyl alcohol at 90 110 DEG C, then steam inclined acid anhydride in 230 250 DEG C of vacuum；(4) it in the solid product incorporation fuel oil obtained step (2), is sent on incinerator and burns；(5) ashes that burning obtains are dissolved in acid solution, filtered；(6) pH value is adjusted to 10 12, must be precipitated, filtering, cleaning obtain metallic compound precipitation.The present invention improves the specific aim and efficiency of black slag separation, recycles the noble metal in inclined acid anhydride and catalyst to greatest extent, preferable economic benefit can simultaneously be obtained by being conducive to environmental protection.
Description
Technical field
The present invention relates to the methods that the by-product generated in a kind of inclined acid anhydride production carries out integrated treatment.
Background technology
Trimellitic anhydride also known as l, 2,4- benzenetricarboxylic acid acid anhydrides, often referred to simply as inclined acid anhydride, in molecular structure containing carboxylic acid and
Acid anhydride structure has both the chemical property of benzoic acid and phthalic anhydride, and generation ester or polyester can be reacted with alcohol, and generation salt is reacted with alkali, with
Ammonia (amine) reaction generation one acid imide of amide, occurs condensation reaction etc. so that it is in production PVC trees under catalyst action with hydrocarbon
The leaching of fat plasticizer, polyimide resin paint, water soluble alkyd resin, epoxy curing agent, low pressure and pulse power container
Stain agent, cinefilm, water treatment agent and surfactant etc. tool have been widely used.
Trimellitic anhydride be earliest by tetraalkyl benzene through gaseous oxidation producing pyromellitic dianhydride when, sent out as by-product
Existing.At present, the production method of trimellitic anhydride mainly has pseudocumene liquid phase nitric acid oxidation method, pseudocumene gas phase air oxygen
Change method, pseudocumene liquid phase air oxidizing process and ask 4 kinds of dimethylbenzene formaldehyde liquid-phase air oxidation (MGC methods).
The inclined acid anhydride of domestic production considers from economy and investment amount, using pseudocumene as raw material, using liquid phase air oxidation
Method.Domestic production device once adds in catalyst mostly using a batch agitator kettle or bubbling column reactor at present, reacts
Temperature drift, although the qualified trimellitic anhydride product that mass fraction is 98% can also be obtained, yield is relatively low, acetic acid consumption
Height lacks Tail gas measuring means, cannot ensure safely, equipment seriously corroded；In crystallization stage, external manufacturer is first
Crystallization and purification is carried out, then be dehydrated into acid anhydride to the oxidation product trimellitic acid of pseudocumene, the granularity of crystal is big, is easily isolated and washes
It washs.And domestic production device that is, by oxidation product Direct Dehydration into acid anhydride, causes product then using the process route of " step into acid anhydride "
Yield significantly declines, and product quality fusing point is relatively low, and international most advanced level is not achieved in yellowish；It is domestic into anhydride process
Manufacturer once easily leads to hot-spot generally using one-pot intermittently operated into acid anhydride, and side reaction increases；When refined, state
Interior producer generally refines trimellitic anhydride using autoclave batch fractionating, and hydrostatic column pressure adds the pressure that higher segregation section generates in kettle
Drop so that the quality and yield of trimellitic anhydride significantly decline.At present, domestic batch production process product yield (mole) exists
50~60% (being fed intake calculating with pseudocumene).
CN1594302A proposes a kind of method of the continuous production trimellitic anhydride of catalysis oxidation step by step, using pseudocumene
For raw material, using low first aliphatic carboxylic acid as solvent, using cobalt, manganese, bromine as catalyst, include the following steps：1) catalysis is continuous step by step
Oxidation process；2) crystallization, solid-liquor separation；3) into anhydride process；4) subtractive process；5) solvent recovery process.It is strong with productive labor
Spend small, product quality is stablized, safe, the features such as product yield is high, is suitable for scale industrial production.
CN1485304A discloses a kind of work with one-step production of high-purity trimellitic acid from pseudocumene (referred to as inclined acid anhydride)
Skill, using inclined acid anhydride, by-product vapour pressure is higher than the spy of inclined acid anhydride vapour pressure under the partial pressure difference during reaction generates gas and same temperature
Point, with passive hot wall sublimate catching apparatus from gas-phase catalysis produce onestep extraction in the gas-phase product that inclined anhydride reactant generates go out it is pure
The inclined anhydride product of degree 99%.
Since current domestic technique is integrally relatively backward, a large amount of by-product is produced, these by-products are more difficult
Separation, often reaction product forms the i.e. so-called black slag of a large amount of by-product after fractionation.In black slag containing it is a certain amount of not
The inclined acid anhydride isolated and the noble metal being dissolved down from catalyst etc. have the product of economic value, additionally contain and are aoxidizing
Other low molecular oxygen-bearing organic matters that stage generates and the heavy polymer generated since dispersion is uneven, these
Material mixing is difficult to detach and handle together, at present both at home and abroad for the recycling of by-product there are no it is relevant report and
Research.
Invention content
Present invention is generally directed to domestic acid anhydride production technologies inclined at present more to fall behind, and generates showing for the black slag of a large amount of by-product
Shape.It proposes a kind of method of comprehensive utilization of black slag, valuable inclined acid anhydride and noble metal component is proposed from black slag, so as to improve enterprise
The economic benefit of industry also significantly reduces pollution and destruction of the production for environment.
It carries out carrying out preliminary analysis to the composition of black slag by means such as UV, FTIR, HPLC.Compare the red of black slag and inclined acid anhydride
External spectrum spectrogram, it can be found that containing inclined acid anhydride in black slag, and also contain other a large amount of substances, in addition to the main spy of inclined acid anhydride in black slag
It levies outside peak, 1781cm the most apparent-1、1854cm-1The characteristic peak at place is mainly open chain acid anhydrides through analyzing the two characteristic peaks
Characteristic peak, 1241cm-1Locate asymmetric C-O-C stretching vibration peaks and also further prove the existing of a large amount of open chain acid anhydrides
Possibility, meanwhile, by the 1009cm in fingerprint peaks area-1、906cm-1、726cm-1Etc. peak type and peak position variation, also can be preliminary
Judge the presence of open chain acid anhydrides, and there is complicated branched structure.The analysis result of HPLC (high performance liquid chromatography) further demonstrates that,
Inclined acid anhydride content in black slag is about 40%.
The present invention proposes a kind of integrated conduct method of the black slag of the generation in inclined acid anhydride production, includes the following steps：(1) it is black
The dissolved solution of slag is in ethanol water, dissolving stirring 1-3h；(2) dissolved product is put into a settling tank carry out it is quiet
It only settles 3-12 hours, after solid-liquid significantly layering, upper solution suction centrifuge is centrifuged with pump, is filtered
Liquid；(3) gained filtrate is distilled, water and ethyl alcohol is first steamed at 90-110 DEG C, is then steamed partially in 230-250 DEG C of vacuum
Acid anhydride；(4) in the solid product incorporation fuel oil obtained step (2), it is sent to incinerator burning；(5) obtained ashes will be burned
It is dissolved in acid solution, filters；(6) pH value is adjusted to 10-12, is precipitated, filters, cleans, obtains metallic compound precipitation.
The mass ratio of black slag and ethanol water is 1 in step (1):2-5, preferably 1:3-3.5.
The mass ratio of second alcohol and water is 0.2-0.5 in step (1) ethanol water:1, preferably 0.3-0.4.
The process of distillation water outlet described in step (3) and ethyl alcohol carries out under normal pressure or reduced pressure, preferably in decompression item
It is carried out under part, preferably vacuum degree is 0.01-0.03MPa.
Fuel oil described in step (4) is gasoline, diesel oil, biodiesel, Fischer-Tropsch synthesis oil, tenor less than 200ppm
It is one or more in the heavy oil of (weight ratio).
The precipitation of metallic compound described in step (6) is the hydroxide of metal or the salt of metal.
Metallic compound can recycle the catalyst for being used to prepare and producing inclined acid anhydride in step (6).
The yield that the method recycles inclined acid anhydride from black slag is 20-40wt%, in terms of the weight of black slag；The inclined acid anhydride of recycling
Purity can reach more than 98wt%.
The present invention by the Accurate Analysis that is formed to black slag, using black slag is dissolved, separation of solid and liquid, then to water-soluble
The method that liquid and solid product are handled respectively improves the specific aim and efficiency of separation, achieves preferable economic benefit.This hair
The it is proposed of bright creativeness dissolves black slag using ethanol water, substantially increases inclined acid anhydride from the dissolution rate in black slag, reduces simultaneously
Part high molecular polymer enters in solution in black slag, reduces and subsequently detaches inclined acid anhydride difficulty from solution.It is generally believed that inclined acid anhydride
Esterification can occur with alcohol, the ester type compound of generation is difficult to detach with inclined acid anhydride, so not using ethyl alcohol as inclined acid anhydride
Detach auxiliary agent.But the present inventor is found surprisingly that, inclined acid anhydride can be greatly improved in ethanol water from the dissolution rate of black slag, this
May be because the concentration of ethyl alcohol reduces, so as to which esterification is more difficult, but under the action of molecular separating force, inclined acid anhydride is from black
Dissolution in slag is more prone to；In addition more complicated oxygen-bearing organic matter may be for the generation of reduction esterification in black slag
It has a certain impact.
Specific embodiment
Embodiment 1
Black 5 parts of slag, 10 parts of the ethanol solution of ethyl alcohol and water quality than 0.2；
(1) the dissolved solution of black slag is in ethanol water, dissolving stirring 1h；(2) dissolved product is put into sedimentation
Quiescent settling is carried out in pond 3 hours, after solid-liquid significantly layering, upper solution suction centrifuge is centrifuged with pump,
Obtain dissolving stirring 1h filtrates；(3) gained filtrate is distilled, first water and ethyl alcohol is steamed in normal pressure, 110 DEG C, then 230
DEG C vacuum steams inclined acid anhydride；(4) it in the solid product incorporation fuel oil obtained step (2), is sent on incinerator and burns；(5) will
Obtained ashes are burned to be dissolved in acid solution, filter；(6) pH value is adjusted to 10, is precipitated, filters, cleans, metallized
Close object precipitation.
Embodiment 2
Black 5 parts of slag, 30 parts of the ethanol solution of ethyl alcohol and water quality than 0.5；
(1) the dissolved solution of black slag is in ethanol water, dissolving stirring 3h；(2) dissolved product is put into sedimentation
Quiescent settling is carried out in pond 10 hours, after solid-liquid significantly layering, upper solution suction centrifuge is centrifuged with pump,
Obtain dissolving stirring 1h filtrates；(3) gained filtrate is distilled, first steams water and ethyl alcohol in vacuum degree 0.02MPa, 90 DEG C,
Then inclined acid anhydride is steamed in 250 DEG C of vacuum；(4) it in the solid product incorporation fuel oil obtained step (2), is sent on incinerator and burns
It burns；(5) ashes that burning obtains are dissolved in acid solution, filtered；(6) pH value is adjusted to 12, is precipitated, filters, cleans, obtain
It is precipitated to metallic compound.
Comparative example 1
Black 5 parts of slag adds in and stirring is dissolved in 70 DEG C of hot water, carries out quiescent settling 10 hours in settling tank, treats that solid-liquid is bright
After aobvious layering, upper solution suction centrifuge is centrifuged with pump, obtains dissolving stirring filtrate；(3) by gained filtrate
It is distilled, first steams water in vacuum degree 0.02MPa, 90 DEG C, then steam inclined acid anhydride in 250 DEG C of vacuum；Inclined acid anhydride yield is
43wt%, purity 84wt%.
Comparative example 2
Black 5 parts of slag is added in 10 parts of straight alcohols, is heated to 70 DEG C of reactions 10h, esterification yield 40-50%, product is carried out
Other impurity can not detach in atmospheric and vacuum distillation, esterification products and black slag.
It can be seen that from above example comparative example using traditional inclined acid anhydride solvent such as water or ethyl alcohol, it can not be effective
It is dissolved from black slag and recycles inclined acid anhydride, and inclined acid anhydride then can effectively be recycled using method of the present invention, achieve expectation
Less than technique effect.
Above example is only the preferred embodiment of the present invention, but present invention is not limited to the embodiments described above,
Without departing substantially from the present invention substantive content in the case of, those skilled in the art can make it is any it is conspicuously improved, replace
It changes or modification is all within the scope of the present invention.
Claims (10)
1. the integrated conduct method of black slag generated in a kind of inclined acid anhydride production, which is characterized in that include the following steps：(1) black slag
Dissolved solution is in ethanol water, dissolving stirring 1-3h；(2) dissolved product is put into a settling tank carry out it is static
Upper solution suction centrifuge after solid-liquid significantly layering, with pump is centrifuged, obtains filtrate by sedimentation 3-12 hours；
(3) gained filtrate is distilled, water and ethyl alcohol is first steamed at 90-110 DEG C, then steams inclined acid anhydride in 230-250 DEG C of vacuum；
(4) it in the solid product incorporation fuel oil obtained step (2), is sent on incinerator and burns；(5) ashes obtained burning are molten
Solution is in acid solution, filtering；(6) pH value is adjusted to 10-12, is precipitated, filters, cleans, obtains metallic compound precipitation.
2. the method as described in claim 1, it is characterised in that the mass ratio of black slag and ethanol water is 1 in step (1):2-
5。
3. method as claimed in claim 2, it is characterised in that the mass ratio of black slag and ethanol water is 1 in step (1):3-
3.5。
4. the method as described in claim 1, it is characterised in that the mass ratio of second alcohol and water is in step (1) ethanol water
0.2-0.5:1。
5. method as claimed in claim 4, it is characterised in that the mass ratio of second alcohol and water is in step (1) ethanol water
0.3-0.4。
6. the method as described in claim 1, it is characterised in that the process of distillation water outlet described in step (3) and ethyl alcohol is in normal pressure
Or it is carried out under reduced pressure.
7. the method as described in claim 1, it is characterised in that fuel oil described in step (4) is gasoline, diesel oil, F- T synthesis
It is one or more in the heavy oil of oil, tenor less than 200ppm.
8. the method as described in claim 1, it is characterised in that the precipitation of metallic compound described in step (6) is the hydrogen-oxygen of metal
The salt of compound or metal.
9. the method as described in claim 1, it is characterised in that metallic compound, which can recycle, in step (6) is used to prepare life
Produce the catalyst of inclined acid anhydride.
10. the method as described in claim 1, it is characterised in that the yield that the method recycles inclined acid anhydride from black slag is 20-
40wt%, in terms of the weight of black slag；More than the purity 98wt% of the inclined acid anhydride of recycling.
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| CN111004374B (en) * | 2019-11-26 | 2021-09-24 | 南通百川新材料有限公司 | Method for preparing alkyd resin based on trimellitic anhydride rectification heavy residual liquid |
| CN114773672A (en) * | 2022-06-05 | 2022-07-22 | 黄山学院 | Low-cost plasticizer for PVC and preparation method thereof |
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| CN1524069A (en) * | 2001-01-19 | 2004-08-25 | Bp | Addition of mineral acids or salts thereof to a TMA production process |
| CN101704734A (en) * | 2009-11-20 | 2010-05-12 | 南京昂扬化工有限公司 | Method for recovering diluted acetic acid in production process of trimellitic anhydride |
| CN102512842A (en) * | 2011-12-16 | 2012-06-27 | 无锡百川化工股份有限公司 | Continuous operation equipment and method for reducing impurity content of trimellitic anhydride |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1524069A (en) * | 2001-01-19 | 2004-08-25 | Bp | Addition of mineral acids or salts thereof to a TMA production process |
| CN101704734A (en) * | 2009-11-20 | 2010-05-12 | 南京昂扬化工有限公司 | Method for recovering diluted acetic acid in production process of trimellitic anhydride |
| CN102512842A (en) * | 2011-12-16 | 2012-06-27 | 无锡百川化工股份有限公司 | Continuous operation equipment and method for reducing impurity content of trimellitic anhydride |
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