CN1195660A - Comprehensive utilization of terephthalic acid residual liquid - Google Patents
Comprehensive utilization of terephthalic acid residual liquid Download PDFInfo
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- CN1195660A CN1195660A CN 97103884 CN97103884A CN1195660A CN 1195660 A CN1195660 A CN 1195660A CN 97103884 CN97103884 CN 97103884 CN 97103884 A CN97103884 A CN 97103884A CN 1195660 A CN1195660 A CN 1195660A
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Abstract
The present invention mainly uses a series of conventional chemical unit operation processes and adopts an ingenious combination mode to treat terephthalic acid residue. After the residue is treated by said invented technological process, a large amount of useable chemical materials can be recovered, and said recovered chemical raw materials mainly include three products of solid terephthalic acid residue, mixture material of cobalt carbonate and manganese carbonate and acetic acid with concentration of above 80%. Besides, said invention adopts a closed circulation technological process for various waste waters produced in the course of production, so that it can greatly reduce sewage discharge.
Description
The present invention relates to the comprehensive utilization of terephthalic acid raffinate, belong to the recycling of chemical industry waste.
The terephthalic acid raffinate is in pure terephthalic acid's device production process, the waste that its oxidation unit discharges.Main at present employing incinerator carries out burning disposal with oil fuel or fuel gas under the high temperature about 1100 ℃.
Because burning method need consume a large amount of oil fuel or fuel gas, and production system is inflammable, explosive, operation easier is big, and working rate is low, also the ample resources of recyclable utilization in the terephthalic acid raffinate is burnt simultaneously, and waste is serious.
The method of comprehensive utilization that the purpose of this invention is to provide a kind of terephthalic acid raffinate, the present invention adopts the means of production of a series of routines in the chemical field, each active principle in the terephthalic acid raffinate is progressively reclaimed, turn waste into wealth, solved a great problem that the puzzlement pure terephthalic acid produces.
The object of the present invention is achieved like this: the present invention mainly adopts technique means such as extraction, filtering separation, evaporation concentration, reaction sedimentation, rectifying, and the solid organic acid in the terephthalic acid raffinate, cobalt manganese, three kinds of components of acetic acid are carried out Separation and Recovery.The composition of terephthalic acid raffinate sees Table 1:
Table 1: the composition * (Wt%) of terephthaldehyde's acid residue liquid
| Sequence number | Liquid phase is formed | Solid phase is formed | Cobalt, manganese in the solid phase | |||||||
| Acetic acid | Water | Phenylformic acid | The acid of terephthaldehyde's base | P-Xylol acid | M-xylene acid | O-Xylol acid | Other | The atom cobalt | Atom manganese | |
| ??1 | ??87.15 | ??12.85 | ??37.96 | ??1.83 | ??45.27 | ??7.97 | ??3.60 | ??0.24 | ??1.15 | ??1.98 |
| ??2 | ??78.65 | ??21.35 | ??32.07 | ??1.59 | ??50.78 | ??7.33 | ??4.35 | ??0.85 | ??1.08 | ??1.95 |
Annotate 1: the solid-to-liquid ratio in the sequence number 1 is 31.6/68.4;
Solid-to-liquid ratio in the sequence number 2 is 37.9/62.1.
2: before analyzing residue liquid is carried out solid-liquid separation.
Concrete recovery method is as follows: the terephthalic acid raffinate that is shipped by tank car, directly pump into vaporizer, with the low-pressure steam of 0.3MPa (table) under the state of 139 ℃ of boiling temperatures, evaporated 2 hours, steam the wherein dilute acetic acid of 60% liquid level, the acetic acid gas phase is collected in the dilute acetic acid groove after condensation is cooled to 35 ℃.Residue contains Cobaltous diacetate, manganese acetate and other organic acid residue material in the vaporizer, uses 0.5m
3Pump into abstraction pool after the water making beating, by adding water and adding the low-pressure steam that is used to heat up, regulate grain slag ratio and extraction temperature in abstraction pool, suitable grain slag ratio is 7: 1, and best extraction temperature is 45 ℃.Simultaneously, the control extraction time is more than 30 minutes, and the employing paddle agitator, and the residue material of keeping in the extractor is suspended state (abstraction pool is an atmospheric operation).
Compound after extraction, the whizzer of using stainless steel separates under the condition of separation factor 645 separating rotating speed 900r/min.SOLID ORGANIC acid sludge under separating directly packs the back export trade, and the aqueous solution of telling that contains Cobaltous diacetate manganese is collected in the medial launder, send the steam of vaporizer with 0.3MPa (table), under the situation of 110 ℃ of boiling temperatures, evaporated 2 hours, steam wherein 2/3 water and acetic acid and be cooled to and be collected in the extraction water of making the residue material in the wastewater disposal basin after 35 ℃ through condensation, and the cobalt manganese solution after concentrating is put into another medial launder, behind naturally cooling, make and be dissolved in wherein 6% SOLID ORGANIC acid crystal and separate out, extract upper clear supernate then and go into reaction tank and add alkali reaction, separate out the solid acid sludge in the pond and regularly pump into abstraction pool and handle again.
Enter the Cobaltous diacetate manganese solution of reaction tank, under the situation of continuously stirring, add soda ash, regulate pH value to 8.5 and stop to add alkali, whether sampling analysis Cobaltous diacetate has wherein all generated cobaltous carbonate, if reaction is not exclusively, then quantitatively add alkali to reaction and finish according to analytical results, and keep 1% excessive.Specific analytical method is as follows: get 2000 milliliters of the interior cobalt manganese solutions of reaction tank, with the terylen filter cloth of 621-90 on B after filtering, get clear liquid and put into container for 1000 milliliters, quantitatively added 1 gram solid soda ash continuously stirring again 5 minutes, soda ash is fully dissolved, left standstill then 30 minutes, and observed the carbonic acid cobalt-manganese salt throw out that redfree is arranged.If do not have, then explanation is reacted and is finished, if there is precipitation to produce, then continues to add alkali, still adds 1 gram as stated above at every turn, when the nothing precipitation is separated out, calculates the total amount that adds alkali.According to the volume of cobalt manganese liquid in the reaction tank, corresponding amplification calculates the quantity that reaction tank should add alkali again.
As get 1000 milliliters of clear liquids and add alkali 3 gram afterreactions and finish existing 50m in the reaction tank
3Cobalt manganese liquid, then reaction tank also need add 150 kilograms in alkali.
After reaction finished, agitator moved continuously, kept cobaltous carbonate manganese to be suspended state, directly sent the stainless steel whizzer with this suspension, separating rotating speed 900r/min, separated under the condition of separation factor 545; If (solid is the mixture of cobaltous carbonate and manganous carbonate to the solid content in the suspension, the solid content analytical procedure is: after getting 1000ml suspension and weighing, filter with B, the filter cake of gained is dried under 120 ℃ condition and was weighed in 15 minutes, the quality of filter cake is a solid content with the ratio of suspension total mass) be lower than 1%, then stop to stir, allow its free setting more than 8 hours, take out the clear liquid on top 1/3 then, be sent from scheming after residue cobalt manganese liquid stirs again again and separate.Isolated alkaline waste water is collected in the wastewater disposal basin, and a part can be used as the additional water of abstraction pool, and redundance send sewage work; Powder material by isolated red cobaltous carbonate of whizzer and manganous carbonate can directly pack the back export trade.
By the dilute acetic acid that vaporizer steams, be collected in the diluted acid jar, after some amount (more than 10 tons), send rectifying tower rectifying.Because of supplied materials discontinuous, so rectifying tower should be designed to batch operation.Cat head distilled water (containing acid below 2%) can extract water, export trade after the concentrated acid entrucking of 90% concentration that the tower still obtains.
The present invention can handle the various terephthaldehyde's acid residue liquid that efflux in pure terephthalic acid's production process, the pollution problem that has thoroughly solved terephthaldehyde's acid residue liquid; Simultaneously, can therefrom reclaim three products of compound, acetic acid of SOLID ORGANIC acid sludge, cobaltous carbonate and manganous carbonates such as terephthalic acid, remarkable in economical benefits.In addition, after device builds up, can solve part labor force's the problem of employment, and the incinerator system of original pure terephthalic acid's device can save all.
Accompanying drawing 1 is a process flow diagram of the present invention.
The invention will be further described with embodiment below in conjunction with accompanying drawing, but the present invention is not limited to this, and spirit of the present invention and protection domain illustrate in appending claims.
Embodiment 1: lab scale embodiment
(1) evaporation:
But get 2000 milliliters of terephthaldehyde's acid residue liquid and put into the vaporizer of temperature control, evaporate under 139 ℃ boiling temperature normal pressure, vaporizer top installs prolong and the logical water coolant of going up additional, and the acetic acid that steams is collected in the container after condensation is cooled to normal temperature.Material does not have acetic acid and steams in vaporizer, and (can be observed the flaky white crystals body of snow blows out) stopped distillation at once when phenylformic acid had just occurred distilling, and reached the purpose of Solid-Liquid Separation.Separating the liquid phase that obtains heavily is: 1546 grams, solid phase is: 712 restrain, and collect calculating solid-liquid ratio mutually according to solid-liquid to be: 0.46: 0.54.The liquid phase dilute acetic acid is as the raw material of rectifying, and the mensuration of its acid concentration can adopt conventional acid base titration, records acid content and is: 79.3% (Wt); The solid phase residue is as the raw material that reclaims cobalt manganese, and it forms the employing high pressure lipuid chromatography (HPLC), and cobalt, manganese quantitatively adopt atomic absorption spectrometry, and the cobalt contents that records in the solid phase is 1.12% (Wt).
The rectifying of liquid phase dilute acetic acid belongs to conventional chemical industry operation, and this lab scale is not done, and the test emphasis is the recovery of cobalt manganese in terephthaldehyde's acid residue.
(2) extraction, separation:
Extraction test is implemented under normal pressure in 1000 milliliters high wall beakers, grain slag ratio by 7: 1, remaining residue material after the above-mentioned evaporation is got 80 grams and 45 ℃ deionized water 560 gram, evenly mixed in beaker, keep 45 ℃ extraction temperature by thermostatic water-circulator bath, under electronic stirring, extract, after extraction in 30 minutes finishes, while hot with B filtrations of bleeding, the filter cake of white is the SOLID ORGANIC acid sludge with the solidliquid mixtures of 640 grams in the beaker, and the filtrate of redness is mother liquor.
(3) reaction, sedimentation, separation:
In order to reduce the alkaline consumption in the reaction process, shorten the reaction times, the red mother liquor of above-mentioned gained carried out evaporation concentration earlier, but with the vaporizer of temperature control at 110 ℃, evaporate under the normal pressure, boil off 2/3 liquid phase, the cobalt manganese liquid after residue concentrates naturally cools to normal temperature, makes wherein dissolved phenylformic acid and phthalic acid, organic acid crystallizations such as terephthalic acid, separate out, again with the B filtration of bleeding, and with the 10ml deionized water to filter cake washing to put forward the cobaltic rate of recovery.Solid acid sludge that filter cake after the filtration and extracting and separating go out merges, and the concentrated solution (containing washings) that filters gained is put into another high wall beaker of 1000 milliliters and added alkali reaction.The whole alkali process that adds needs continuously stirring.When initially adding alkali, because Na
2CO
3With emit CO behind wherein the organic acid reaction
2, a large amount of foams can appear in beaker top, and add alkali speed this moment will control well, and each 1 gram is treated to add behind the lather collapse again, prevents to overflow.When non-foam occurs when adding soda ash, show that the acid-base neutralisation reaction finishes, answer the limit to add the pH value of alkali limit with PH test paper test reaction liquid, when pH value to 8.0 the time, should slowly add alkali, pH value was by 9 o'clock, reaction is basic to be finished, and can stop to add alkali this moment, stirs and stops after 5 minutes to stir, after leaving standstill 30 minutes, get upper clear supernate and add 3mgNa for 10 milliliters
2CO
2Observation has or not red precipitate, then continues to add alkali reaction in beaker if having, until terminal point.The cobalt manganese mixed solution of reaction after finishing separates obtaining red cobaltous carbonate manganese blended stock through B filtrations of bleeding, and record quality after the drying (130 ℃, 20 minutes) and be: 5.63 restrain, and cobalt contents is 15.6% (wt).
The rate of recovery of this test cobalt:
Embodiment 2: pilot scale embodiment, charging capacity one car, 9.6m
3, 10.8t, solid-to-liquid ratio is: 0.4: 0.6.
(1) evaporation:
The terephthaldehyde's acid residue that is shipped by tank car divides 6 batches to pump into 2m
3Have in the vaporizer of agitator each charging 1.6m
3, steam wherein dilute acetic acid with the low-pressure steam of 0.3MPa (table).Evaporating initial boiling temperature is 121 ℃, and the terminal point boiling temperature is 139 ℃, steams the acetic acid gas phase and is collected in the dilute acid bath after condensation is cooled to 35 ℃.Acetic acid steams remaining Cobaltous diacetate, manganese acetate and other organic acid residue material of containing in the finisher, uses 0.1m
3Pump into abstraction pool after the water making beating and continue to stir, vaporizer advances second batch of material again and continues evaporation operation.
(2) rectifying:
Send a small-sized packing tower to carry out conventional batch fractionating operation the above-mentioned dilute acetic acid that steams.Tower diameter is Φ 300mm, and filler is 12m for the wire mesh packing height, and heating steam is 0.5MPa (table), normal tower still service temperature is 121 ℃, tower top temperature is 102 ℃, control cat head acid content≤2%, and tower still acid content reaches and is qualified product more than 90%.
(3) extraction, separation:
The Cobaltous diacetate manganese of in batches being sent in the abstraction pool by vaporizer contains organic acid sludge material, adds water to 33m
3(promptly regulate liquid-solid ratio and be about 7: 1) also adds low-pressure steam and regulates when extraction temperature is 45 ℃ and stop steam, stirs after 30 minutes, carries out solid-liquid separation to the whizzer charging, and centrifuge speed is 900r/min, and separation factor is 645.
Isolated mother liquor is collected in the medial launder, and divides 16 batches to send into vaporizer and boil off 2/3 liquid phase, and vaporization temperature is 110 ℃, and evaporation time is 2 hours/batches.Cobalt manganese liquid after the evaporation concentration is placed in the crystallizer tank, makes it naturally cool to normal temperature, and cooling back clear liquid send reaction tank, and the SOLID ORGANIC acid sludge liquid that crystallization is separated out is delivered to whizzer again and carried out secondary separation, and adds 0.01m
3Water washing filter cake (can return abstraction pool when producing greatly, needn't carry out secondary separation), the clear liquid of telling directly send reaction tank, all isolated SOLID ORGANIC acid residue packs.
(4) reaction, sedimentation, separation:
Through concentrating, the cobalt manganese solution after the separation is 10.2m altogether
3, all be collected in 20m
3Have in the reaction tank of agitator.Turn on agitator, add solid soda ash, add one bag (40kg), when initially adding alkali at every turn, the pond inner foam is more, should treat to add second bag again after foam disappears substantially, when non-foam occurs in adding to reaction tank, show that the acid-base neutralisation reaction finishes, pH value arrives 7, at this moment, add alkali number is 20kg (half bag) at every turn, stirs and measures a pH value after 10 minutes.When pH value reaches 8, according to following sampling and analyzing method, determine to add alkali number, add 10kg at every turn, stirred 10 minutes, after adding the alkali end, stirred 30 minutes, then feed liquid is directly sent into the whizzer of stainless steel,, carried out lock out operation under the condition of separation factor 545 separating rotating speed 900r/min.
Analytical procedure is as follows: get 2000 milliliters of the interior cobalt manganese solutions of reaction tank, with the filtration of on B, bleeding of the terylen filter cloth of 621-90, the clear liquid of getting after the filtration is put into container for 1000 milliliters, quantitatively added 1 gram solid soda ash continuously stirring again 5 minutes, soda ash is fully dissolved, left standstill then 30 minutes, and observed the carbonic acid cobalt-manganese salt throw out that redfree is arranged.If do not have, then the explanation reaction finishes; As if there being precipitation to produce, then continue to add alkali, still, when the nothing precipitation is separated out, calculate the total amount that adds alkali by the method for each 1 gram.According to the volume of cobalt manganese liquid in the reaction tank, corresponding amplification calculates the quantity that reaction tank should add alkali again.
As get the 1000ml clear liquid and add alkali 5g afterreaction and finish existing 10.2m in the reaction tank
3Cobalt manganese liquid, then reaction tank also need add alkali 51kg.
The alkaline waste water of being told by whizzer drains into sewage work's (can be used as extraction when producing greatly and add water) and the pressed powder material that obtains is a cobalt manganese blended stock, all packs.
This pilot scale products obtained therefrom amount is:
Acetic acid: 90.2%, 5.27t
Cobalt manganese blended stock: contain cobalt 10.1%, 48.1kg
Solid organic acid: 5.1t (not analyzing)
Consumption alkali (solid soda ash): 240kg
Application examples: by raising the self-raised fund of sub-petrochemical industry repair company, the cover scale of building up is 2000 tons/year a device in the present invention, test run in January, 96, and formally put into operation May, now oepration at full load.From nearly half a year of many conditions of production, this device can be handled by raising the Subsidiary Company chemical plant and produce about 8000 tons/year of all terephthaldehyde's acid residue liquid that 450,000 tons of pure terephthalic acid's devices efflux per year, about 2600 tons of annual recyclable SOLID ORGANIC acid sludge, 80 tons of Co-Mn mixtures (containing cobalt more than 10%).Acetic acid about 5000 tons (acid content is more than 80%), about 4,800,000 yuan of normal year sales revenue; Remove labor wage, equipment amortization, the energy various expenditures such as disappear, annual return is more than 1,500,000 yuan; 5,200,000 yuan of project gross investments, 3.5 years static payback times.In addition, solved 30 worker children's the problem of employment, the operation that can save pure terephthalic acid's device incinerator simultaneously, the sewage disposal expenses of maintenance cost and water factory etc. are annual more than 1,000 ten thousand yuan.
Claims (2)
1. the method for comprehensive utilization of terephthalic acid raffinate is characterized in that this method comprises:
(1) evaporation: but the terephthalic acid raffinate is put into the vaporizer of temperature control, use 0.3MP
aThe low-pressure steam of (table) was evaporated 2 hours under the state of 139 ℃ of boiling temperatures, and the acetic acid that steams is collected in the container after condensation is cooled to normal temperature;
(2) extraction, separation: will pump into abstraction pool after the making beating of the material water in the container, in abstraction pool by adding water and adding the low-pressure steam be used to heat up, regulate grain slag ratio and extraction temperature, the control extraction time is more than 30 minutes, and employing paddle agitator, the residue material of keeping in the extractor is suspended state, and the compound after extraction separates with whizzer; SOLID ORGANIC acid sludge under separating directly packs export trade, and the remaining aqueous solution that contains Cobaltous diacetate manganese is collected in the medial launder, continuing vapourisation under reduced pressure concentrates, and the cobalt manganese solution after concentrating is put into another medial launder, behind naturally cooling, make and be dissolved in wherein the SOLID ORGANIC acid crystal of 6% (weight) and separate out, extract upper clear supernate then and go into reaction tank and add alkali reaction, the solid acid sludge of separating out in the pond regularly pumps into abstraction pool and handles again;
(3) reaction, sedimentation, separation: enter the Cobaltous diacetate manganese solution in the reaction tank, under the situation of continuously stirring, add soda ash, regulate pH value to 8.5 and stop to add alkali, sampling analysis, after reaction finishes, agitator moves continuously, and this suspension is sent from the scheming separation, if the solid content in the suspension is lower than 1%, then stop to stir, allow its free setting more than 8 hours, take out the clear liquid on top 1/3 then, be sent from scheming after residue cobalt manganese liquid stirs again again and separate.
2, method according to claim 1 is characterized in that described grain slag ratio is 7: 1, and described extraction temperature is 45 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103884A CN1059892C (en) | 1997-04-04 | 1997-04-04 | Comprehensive utilization of terephthalic acid residual liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97103884A CN1059892C (en) | 1997-04-04 | 1997-04-04 | Comprehensive utilization of terephthalic acid residual liquid |
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| CN1195660A true CN1195660A (en) | 1998-10-14 |
| CN1059892C CN1059892C (en) | 2000-12-27 |
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|---|---|---|---|
| CN97103884A Expired - Fee Related CN1059892C (en) | 1997-04-04 | 1997-04-04 | Comprehensive utilization of terephthalic acid residual liquid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843630B (en) * | 2005-04-08 | 2010-05-12 | 三井化学株式会社 | Method for reclaiming oxidation catalyst |
| CN101152969B (en) * | 2006-09-29 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | Method of processing p-benzene dicarboxylic acid production wastewater |
| CN102381963A (en) * | 2011-08-04 | 2012-03-21 | 绍兴县金程针纺有限公司 | Method and device for preparing benzoic acid by utilizing waste PX (paraxylene) oxidation residues |
| CN101268034B (en) * | 2005-08-11 | 2012-07-11 | 奇派特石化有限公司 | Process for removal of benzoic acid from an oxidizer purge stream |
| CN102786412A (en) * | 2012-09-03 | 2012-11-21 | 绍兴汉青环保科技有限公司 | Extraction method for extracting benzoic acid, p-toluic acid, terephthalic acid and isophthalic acid from pure terephthalic acid (PTA) oxidation residues |
| CN107879953A (en) * | 2017-10-28 | 2018-04-06 | 南通江山农药化工股份有限公司 | Phenyl guanidine carbonate recovery method and its device in waste water |
| CN108569963A (en) * | 2018-05-02 | 2018-09-25 | 广东广益科技实业有限公司 | A kind of production technology of palmitic acid waste residue recycling |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1003650A (en) * | 1963-04-05 | 1965-09-08 | Teijin Ltd | Process for producing purified terephthalic acid |
| DE3328543A1 (en) * | 1983-08-08 | 1985-03-21 | Klöckner-Humboldt-Deutz AG, 5000 Köln | Use of a screen-bowl screw conveyor centrifuge for the separation of fine crystalline solids from a liquid |
-
1997
- 1997-04-04 CN CN97103884A patent/CN1059892C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1843630B (en) * | 2005-04-08 | 2010-05-12 | 三井化学株式会社 | Method for reclaiming oxidation catalyst |
| CN101268034B (en) * | 2005-08-11 | 2012-07-11 | 奇派特石化有限公司 | Process for removal of benzoic acid from an oxidizer purge stream |
| CN101152969B (en) * | 2006-09-29 | 2011-01-19 | 中国石油化工股份有限公司石油化工科学研究院 | Method of processing p-benzene dicarboxylic acid production wastewater |
| CN102381963A (en) * | 2011-08-04 | 2012-03-21 | 绍兴县金程针纺有限公司 | Method and device for preparing benzoic acid by utilizing waste PX (paraxylene) oxidation residues |
| CN102786412A (en) * | 2012-09-03 | 2012-11-21 | 绍兴汉青环保科技有限公司 | Extraction method for extracting benzoic acid, p-toluic acid, terephthalic acid and isophthalic acid from pure terephthalic acid (PTA) oxidation residues |
| CN102786412B (en) * | 2012-09-03 | 2014-09-03 | 绍兴汉青环保科技有限公司 | Extraction method for extracting benzoic acid, p-toluic acid, terephthalic acid and isophthalic acid from pure terephthalic acid (PTA) oxidation residues |
| CN107879953A (en) * | 2017-10-28 | 2018-04-06 | 南通江山农药化工股份有限公司 | Phenyl guanidine carbonate recovery method and its device in waste water |
| CN107879953B (en) * | 2017-10-28 | 2023-07-28 | 南通江山农药化工股份有限公司 | Method and device for recycling phenylguanidine carbonate in wastewater |
| CN108569963A (en) * | 2018-05-02 | 2018-09-25 | 广东广益科技实业有限公司 | A kind of production technology of palmitic acid waste residue recycling |
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|---|---|
| CN1059892C (en) | 2000-12-27 |
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