CN111039776A - High-purity mixed long carbon chain dicarboxylic acid and preparation method thereof - Google Patents
High-purity mixed long carbon chain dicarboxylic acid and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 248
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 200
- 239000002253 acid Substances 0.000 claims abstract description 151
- 239000000463 material Substances 0.000 claims abstract description 78
- 239000012535 impurity Substances 0.000 claims abstract description 77
- 238000003756 stirring Methods 0.000 claims abstract description 67
- 238000001816 cooling Methods 0.000 claims abstract description 66
- 239000000047 product Substances 0.000 claims abstract description 64
- 239000008367 deionised water Substances 0.000 claims abstract description 62
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 62
- 238000001914 filtration Methods 0.000 claims abstract description 58
- 239000012043 crude product Substances 0.000 claims abstract description 45
- 238000010438 heat treatment Methods 0.000 claims abstract description 33
- 238000007670 refining Methods 0.000 claims abstract description 30
- -1 alcohol amine salt Chemical class 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 252
- 238000005406 washing Methods 0.000 claims description 101
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- 239000002904 solvent Substances 0.000 claims description 43
- 238000001035 drying Methods 0.000 claims description 41
- 239000012046 mixed solvent Substances 0.000 claims description 38
- 239000012452 mother liquor Substances 0.000 claims description 36
- 238000000926 separation method Methods 0.000 claims description 30
- 238000002844 melting Methods 0.000 claims description 29
- 230000008018 melting Effects 0.000 claims description 29
- 239000000284 extract Substances 0.000 claims description 27
- 238000000605 extraction Methods 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 22
- 238000011084 recovery Methods 0.000 claims description 22
- 238000004064 recycling Methods 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 17
- 238000001953 recrystallisation Methods 0.000 claims description 17
- 238000003860 storage Methods 0.000 claims description 17
- 238000005191 phase separation Methods 0.000 claims description 16
- 238000004042 decolorization Methods 0.000 claims description 14
- 239000002002 slurry Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 12
- 150000001721 carbon Chemical group 0.000 claims description 10
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- 238000004321 preservation Methods 0.000 claims description 10
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- 239000008346 aqueous phase Substances 0.000 claims description 7
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 6
- 239000002173 cutting fluid Substances 0.000 claims description 4
- 239000010687 lubricating oil Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 229910017052 cobalt Inorganic materials 0.000 abstract description 3
- 239000010941 cobalt Substances 0.000 abstract description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 235000011054 acetic acid Nutrition 0.000 description 68
- 239000004677 Nylon Substances 0.000 description 17
- 238000002386 leaching Methods 0.000 description 17
- 229920001778 nylon Polymers 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000000855 fermentation Methods 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 230000004151 fermentation Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 241000402754 Erythranthe moschata Species 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- DXNCZXXFRKPEPY-UHFFFAOYSA-N tridecanedioic acid Chemical group OC(=O)CCCCCCCCCCCC(O)=O DXNCZXXFRKPEPY-UHFFFAOYSA-N 0.000 description 4
- 239000000052 vinegar Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
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- 239000003205 fragrance Substances 0.000 description 3
- 229960004675 fusidic acid Drugs 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001243 acetic acids Chemical class 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 238000010079 rubber tapping Methods 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RZUDZAJRBFRQLS-UHFFFAOYSA-N 2-dodecylpropanedioic acid Chemical compound CCCCCCCCCCCCC(C(O)=O)C(O)=O RZUDZAJRBFRQLS-UHFFFAOYSA-N 0.000 description 1
- TYNLGDBUJLVSMA-UHFFFAOYSA-N 4,5-diacetyloxy-9,10-dioxo-2-anthracenecarboxylic acid Chemical compound O=C1C2=CC(C(O)=O)=CC(OC(C)=O)=C2C(=O)C2=C1C=CC=C2OC(=O)C TYNLGDBUJLVSMA-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 241000222120 Candida <Saccharomycetales> Species 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- ALHUZKCOMYUFRB-OAHLLOKOSA-N Muscone Chemical compound C[C@@H]1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-OAHLLOKOSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- 241000221095 Simmondsia Species 0.000 description 1
- 235000004433 Simmondsia californica Nutrition 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 125000004442 acylamino group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 229960004590 diacerein Drugs 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical class [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000009456 molecular mechanism Effects 0.000 description 1
- ALHUZKCOMYUFRB-UHFFFAOYSA-N muskone Natural products CC1CCCCCCCCCCCCC(=O)C1 ALHUZKCOMYUFRB-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920013636 polyphenyl ether polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a high-purity mixed long carbon chain dicarboxylic acid and a preparation method thereof, which comprises the steps of firstly adding deionized water into a heavy component material raw material, heating while stirring, standing for layering, and removing impurities of a short carbon chain mixed acid with a lower layer in a molten state; then, cooling the upper layer extracting solution, crystallizing and filtering to obtain a crude product; recrystallizing, refining and purifying the obtained crude product to obtain high-purity mixed long carbon chain dicarboxylic acid; the product quality reaches the following technical indexes: the total acid (calculated by the main product of the long carbon chain dicarboxylic acid) is more than or equal to 99.00 wt%, and the color of the platinum and the cobalt is less than 10. Provides a mixed long carbon chain dicarboxylic acid product which has high purity and good color and can meet the requirements of synthesizing industrial products such as dibasic acid salt surfactant, alcohol amine salt antirust and wear-resistant agent, artificially synthesized joss stick and the like as synthesis raw materials, and a preparation method thereof.
Description
Technical Field
The invention relates to high-purity mixed long carbon chain dicarboxylic acid and a preparation method thereof. Belonging to the purification treatment of acyclic dicarboxylic acid with more than 10 carbon atoms.
Background
Long-carbon chain dicarboxylic acid (straight-chain dicarboxylic acid) with a carbon chain containing more than 10 carbon atoms is an important fine chemical product. It is used as main material for synthesizing polyamide resin, polyester resin, hot melt adhesive, perfume, weather resisting plasticizer, lubricant additive, paint, liquid crystal, etc.
The main industrial applications include the artificial synthesis of muscone; coil adhesives used at 100 ℃ for a long time; hot-melt adhesive for shaping clothes; not only can be used for manufacturing a high-temperature-resistant lubricant, but also can be used for manufacturing a lubricant which can realize effective lubrication at a low temperature of minus 45 ℃; the high-performance paint prepared from the long carbon chain dibasic acid has the characteristics of bright color, good wear resistance, high impact strength, strong adhesive force, good flexibility, long-time ultraviolet irradiation resistance and the like. It is suitable for use as paint for sedan, luxurious furniture, national defense tent, military combat and transport means. The long carbon chain dibasic acid can also synthesize the plasticizer with excellent cold resistance, and the plastic film manufactured by adding the plasticizer can be used for a long time in a cold environment.
Nylon is a kind of high molecular compound whose molecular main chain contains amide group (-NHCO-). The nylon molecular structure contains a large amount of acylamino, and the tail end of a macromolecule is amino or carboxyl, so that the nylon is a crystalline polymer which has strong polarity, can form hydrogen bonds among molecules and has certain reaction activity. The nylon is one of five engineering plastics (nylon, polyformaldehyde, polycarbonate, polyphenyl ether and polybutylene terephthalate) with the largest consumption, the largest variety, the widest application and the oldest qualification,
the molecular mechanism of long-chain nylon endows the long-chain nylon with good comprehensive performance, the strength is higher than that of metal, the mechanical performance, the heat resistance, the wear resistance, the chemical resistance, the flame retardance and the self-lubrication are excellent, the friction coefficient is low, the processing is easy, and the long-chain nylon can be processed into various plastic products, also can be drawn into fibers, and also can be processed into films, coatings, adhesives and the like. The method is widely applied to the fields of automobiles, electronics, electrics, machinery, communication, military, aerospace and the like.
Long carbon chain nylon synthesized by using long carbon chain dicarboxylic acid as a raw material and performing polycondensation reaction between a polycondensation monomer and diamine mainly comprises nylon 11, nylon 12, nylon 612, nylon 1111, nylon 1112, nylon 1212, nylon 1213, nylon 1314, nylon 1414, nylon 512, nylon 614 and the like.
The long carbon chain dicarboxylic acid does not exist in the nature, is mainly prepared by an organic synthesis method and a biological fermentation method, and has the advantages of long process route, high cost, low yield, potential safety hazard and environmental pollution.
The biological fermentation method mainly comprises the following steps of11～C18Normal alkane is used as a raw material, and is fermented by candida to convert monoalkyl into long-chain dibasic acid, and then the long-chain dibasic acid is obtained by crude purification and refining. The n-alkane is distilled from petroleum refining and contains C11～C18The component (A) is a by-product obtained by degreasing petroleum by adopting a urea process, and is commonly called liquid paraffin. Therefore, the long-chain dicarboxylic acid produced by the method has the advantages of wide raw material source, simple production process, small investment and low production cost. Therefore, most of the long carbon chain dibasic acids sold in the market at present are products produced by a biological fermentation method.
The purity and appearance of the product are seriously affected because the fermentation product contains a small amount of impurities such as mycoprotein, pigment, iron ion compounds and the like. Therefore, the refining and purifying process is a crucial link for preparing the long carbon chain dicarboxylic acid by microbial fermentation.
The long carbon chain dicarboxylic acid produced by the microbial fermentation method is purified and refined by recrystallization mainly by a solvent method. The solvent mainly adopts acetic acid, methanol and the like. Tests and production practices show that acetic acid is superior to other organic solvents in refining time, refining solvent consumption and purity of crystallized products.
Therefore, in the prior art, the long carbon chain dicarboxylic acid produced by microbial fermentation is purified and purified by a recrystallization method mainly using acetic acid as a solvent. Comprises the process steps of crude product dissolution, decoloration and filtration, cooling and crystallization, centrifugal filtration, filter cake washing, drying and the like. In addition, the method also comprises the recycling of the mother liquor of the long carbon chain dicarboxylic acid refining crystallization.
In the purification and refining process of the long carbon chain dicarboxylic acid, after cooling crystallization and centrifugal filtration, the generated crystallization mother liquor is removed from solvent acetic acid and products which are dissolved in the acetic acid and can not form crystalsIn addition to the long carbon chain dicarboxylic acids, C produced during fermentation10～C18Other long carbon chain dicarboxylic acids with different carbon chain lengths are referred to in the industry as mixed long carbon chain dicarboxylic acids, wherein the mixture of various long carbon chain dicarboxylic acids dissolved in the long carbon chain dicarboxylic acid refining crystallization mother liquor is called as mixed long carbon chain dicarboxylic acids.
In the purification and refining process of the long carbon chain dicarboxylic acid, the acetic acid mother liquor after recrystallization firstly enters a rectification system to recover acetic acid. After acetic acid is recovered, the mass percentage content of the mixed long carbon chain dicarboxylic acid in the generated rectification heavy component is between 40% and 80%, in addition, the heavy component also contains solvent acetic acid and other impurities, and the heavy component can be used as a raw material for preparing the mixed long carbon chain dicarboxylic acid.
The industrial use of mixed long carbon chain dicarboxylic acids is also very widespread. And C10～C18Compared with the application of each long carbon chain dicarboxylic acid industrial product, the long carbon chain dicarboxylic acid can be used in other application fields of long carbon chain dicarboxylic acid except that the long carbon chain dicarboxylic acid industrial product is not suitable for being used as a polymerization monomer, and various industrial products prepared by taking the long carbon chain dicarboxylic acid as a raw material have outstanding surface activity, antirust and wear-resistant performance and high and low temperature lubricating resistance; the perfume prepared from the raw material has musk fragrance, and can be used as musk type perfume. For example:
1. the dibasic acid salt surfactant generated by the reaction of the mixed long-carbon-chain dicarboxylic acid and the alkali can be used for preparing a detergent with excellent quality;
2. the alcohol amine salt of the mixed long carbon chain dicarboxylic acid has excellent antirust and wear-resistant properties. The undecane diacid hydramine salt has the best antirust performance, and can be used as a water-soluble antirust and antiwear multifunctional additive in a metal cutting fluid formula. The prepared environment-friendly high-performance semisynthetic cutting fluid. The cutting tool can be used for various cutting processing of difficult-to-process materials such as high-temperature alloy steel, nickel alloy, titanium alloy and various aluminum alloys, such as turning, boring, milling, drilling, tapping, broaching, tapping and the like, can completely meet the requirements of processing materials and processes, prolongs the service life of the tool, improves the processing efficiency, and has good application prospect.
The mixed long-chain dibasic acid reacts with the mixed alcohol amine, and is compounded with the alkyl succinic anhydride, so that the prepared composite antirust agent has excellent antirust performance, and can meet the cutting processing of cast iron with extremely high antirust requirements.
3. Diester synthesized with octanol is base stock for preparing high-grade lubricating oil, has outstanding high and low temperature resistance, can still keep good lubricating effect at minus 45 ℃, and is suitable for jet engines, gas turbines and high-altitude and high-cold areas;
4. the major raw material for synthesizing the jojoba T is tridecanedioic acid (also called brassylic acid), the tridecanedioic acid and ethylene glycol are firstly condensed to generate the poly-vinegar, then the linear poly-vinegar is depolymerized and cyclized to generate a crude product, and the crude product is refined and purified to obtain the final product. A series of long-chain di-fusidic acid ethylene vinegar can be obtained by adopting long-chain di-fusidic acid with different carbon numbers to perform polycondensation with ethylene glycol, or mixed di-carboxylic acid ethylene vinegar can be obtained by adopting mixed long-chain di-fusidic acid to perform polycondensation with ethylene glycol, the products have musk fragrance and can be used as musk type spices, wherein the fragrance of the first censer synthesized by taking tridecanedioic acid as a raw material is the strongest, and the effect is the best. Is an artificially synthesized large-ring diacerein continue spice.
In the application, compared with the industrial product adopting single long carbon chain dicarboxylic acid, the production cost of the mixed long carbon chain dicarboxylic acid is lower, and the market competitiveness of the corresponding product is favorably improved. In view of the above, the mixed long carbon chain dicarboxylic acid prepared by using the mixed long carbon chain dicarboxylic acid dissolved in the long carbon chain dicarboxylic acid refined crystallization mother liquor as the raw material has a wide market prospect.
In the prior art, the preparation method of the mixed long carbon chain dicarboxylic acid roughly comprises the following two methods:
1. firstly, concentrating the crystallization mother liquor to 1/10-1/4 with the volume being equal to the original volume, and recovering part of the solvent. And then, after concentration, cooling and crystallizing the residual heavy components, and washing and drying the separated crystals to obtain the mixed long carbon chain dicarboxylic acid product.
2. The mother liquor of the long carbon chain dicarboxylic acid refining crystallization is only used for recovering most of the solvent, the rest heavy components are naturally dried until the moisture content is less than or equal to 14 percent, and then the crystallization is carried out after two times of decolorization and one time of acidification treatment. And preparing a mixed long carbon chain dicarboxylic acid product.
The prior art has the following defects:
1. the mixed long carbon chain dicarboxylic acid product prepared by the prior art has high impurity content and high chroma. It is difficult to meet the technical requirements of users.
2. The short carbon chain mixed dicarboxylic acids of less than 9 carbon atoms that are concomitantly produced during fermentation, which have not been removed in the prior art preparation methods, are a major impurity in the mixed long carbon chain dicarboxylic acid product. The existence of the impurities leads the mixed long carbon chain dicarboxylic acid product in the prior art to be difficult to use as a synthetic raw material.
3. The natural drying method wastes solvent resources, occupies valuable land, and pollutes the atmosphere and the water environment. As will be apparent. Naturally airing the heavy rectification components from 50% of moisture content to within 15%, and enabling the rest 15% of moisture to enter a sewage treatment system along with crystallization mother liquor in a subsequent treatment process.
Namely, about 0.35 ton of moisture gas (acetic acid) per ton of rectified heavy component is dissipated into air, and 0.15 ton of moisture liquid enters a sewage treatment system. According to the prior art, about 0.4 ton of long carbon chain mixed dibasic acid can be produced per ton of heavy component in rectification, namely 0.875 ton of acetic acid gas escapes into the air per 1 ton of long carbon chain mixed dibasic acid in production, so that the waste of acetic acid solvent is caused, and the atmospheric environment pollution is also caused. 0.375 ton of acetic acid was fed into the sewage treatment system, which undoubtedly also increased the sewage treatment load.
4. The method of natural drying, neutralization and salifying dissolution, two-time decolorization and acidification crystallization by adding sulfuric acid has complex process. The product chroma is difficult to meet the user requirement.
The total acid content of the mixed long-carbon-chain dicarboxylic acid obtained by the prior art calculated by the refined target long-carbon-chain dicarboxylic acid main product is less than or equal to 85 percent, the total nitrogen content is more than or equal to 160ppm, the ash content is more than or equal to 200ppm, and the chromaticity of platinum and cobalt is more than 85.
5. Because the solvent has a decisive influence on the decoloring effect of the activated carbon, the decoloring effect of the activated carbon on the aqueous solution is far less than that of the organic solution. Therefore, although two times of decolorization are adopted in the decolorization process, the problem of deep chroma of the rectification heavy component is still difficult to solve, and the chroma of the platinum and the cobalt of the mixed long carbon chain dicarboxylic acid obtained by the method is generally more than 85.
The preparation method of the mixed long-carbon-chain dicarboxylic acid has high purity, good color and luster, high yield, low cost, resource conservation and environmental protection, can meet the requirements of using the mixed long-carbon-chain dicarboxylic acid product as a synthetic dibasic acid salt surfactant, an alcohol amine salt antirust anti-wear agent or a synthetic champignon-T synthetic raw material, and is expected by people.
Disclosure of Invention
The invention aims to avoid the defects in the prior art and provide a mixed long carbon chain dicarboxylic acid product which has high purity and good color and can meet the requirements of synthesizing a dibasic acid salt surfactant, an alcohol amine salt antirust wear-resistant agent or a synthesized cinnabar-T synthetic raw material.
The invention also aims to provide the preparation method of the mixed long carbon chain dicarboxylic acid, which has the advantages of high yield, low cost, resource saving and environmental protection.
The object of the invention can be achieved by the following measures:
the high-purity mixed long-carbon-chain dicarboxylic acid is prepared by taking heavy component materials as raw materials, wherein heavy component materials are obtained by filtering mother liquor through recrystallization generated in the recrystallization refining process of industrial long-carbon-chain dicarboxylic acid and recovering acetic acid as a solvent; the method is characterized by comprising the following steps of firstly adding deionized water into the heavy component material raw materials, heating while stirring, extracting mixed long carbon chain dicarboxylic acid into a solution, standing for layering, and removing impurities of short carbon chain mixed acid with a lower layer in a molten state; then, cooling the upper layer extracting solution, crystallizing and filtering to obtain a crude product; recrystallizing, refining and purifying the obtained crude product to obtain high-purity mixed long carbon chain dicarboxylic acid; the product quality reaches the following technical indexes:
the high-purity mixed long-carbon-chain dicarboxylic acid has high main component content, low impurity content and low chroma, and all product quality technical indexes can meet the preparation requirements of various industrial products taking the high-purity mixed long-carbon-chain dicarboxylic acid as a raw material.
The object of the invention is also achieved by the following measures:
the heavy component material of the high-purity mixed long carbon chain dicarboxylic acid is C11～C18In the refining and purifying process of the long carbon chain dicarboxylic acid, generated recrystallization filtration mother liquor is subjected to solvent acetic acid recovery, and heavy components are left at the bottom of the distillation still.
The preparation method of the high-purity mixed long carbon chain dicarboxylic acid comprises the following operation steps:
first step of removing short carbon chain mixed acid impurities
① extraction by water extraction
And (3) putting the heavy component material into a phase separation tank provided with a temperature control device, adding deionized water, and controlling the adding amount to be equal to the weight of the heavy component material: deionized water wt ═ 1: 0.5-1: 3.5 is between; heating to 70-98 ℃ under stirring, carrying out elutriation and extraction for 1-2 hours at the temperature of 70-98 ℃, extracting the mixed long-carbon-chain dibasic acid into an acetic acid and water mixed solvent, and simultaneously melting impurities of the short-carbon-chain mixed acid to be in a molten state;
② standing for layering
Standing for 1-2 hours at the temperature of 70-98 ℃ under heat preservation until materials are layered, wherein the upper layer is an acetic acid and water mixed solvent extract of mixed long carbon chain dicarboxylic acid, and the lower layer is short carbon chain mixed acid melt impurities with a low melting point and carbon atom number less than or equal to 9;
③ removal of short carbon chain mixed acid impurities
Discharging ② layered impurities of the low-melting-point short-carbon-chain mixed acid melt with the carbon number less than or equal to 9 at the lower layer from the bottom of the layering tank, collecting, and performing post-treatment;
second step preparation of mixed long carbon chain dibasic acid crude product
① cooling crystallization
Slowly cooling the acetic acid and water mixed solvent extract of the mixed long carbon chain dibasic acid from which the impurities are removed in the first step to be less than or equal to 30 ℃ in a crystallization kettle under stirring, so that the mixed long carbon chain dibasic acid is crystallized and separated out;
② filtration and separation
Filtering and separating materials from item ① by a plate-and-frame filter press, and removing filtered mother liquor into a solvent recovery system, wherein a filter cake is a crude product of the mixed long-carbon chain dicarboxylic acid;
the third step is the refining of the mixed long carbon chain dibasic acid
① dissolving and decolorizing
a. Dissolution
And (3) putting the mixed long carbon chain dibasic acid crude product prepared in the second step into a dissolving and decoloring reaction kettle, and mixing the mixed long carbon chain dibasic acid crude product with the following components in percentage by weight: acetic acid wt ═ 1: 0.8-1: 3.0, adding acetic acid, stirring, heating to 80-100 ℃, keeping the temperature and dissolving completely for decolorization;
b. decolorizing and filtering
And (b) adding activated carbon into the material dissolved in the item a in a decoloring kettle, wherein the adding amount is controlled in a way that the mass ratio of the crude product to the activated carbon is 1: 0.05-1: between 0.1; stirring, keeping the temperature and decoloring for 0.5-2 hours, then filtering by using a plate-and-frame filter press, and transferring filtrate into a crystallizing tank for crystallization;
② crystallizing by cooling
Naturally cooling the filtrate after the decolorization treatment to 50-75 ℃ under stirring in a crystallizing tank; then, gradually opening a circulating cooling water valve to reduce the temperature of the materials in the crystallizing tank to be less than or equal to 30 ℃ until the crystallization is complete;
③ centrifuging and separating
And (5) putting the materials in the crystallization tank into a centrifugal machine for solid-liquid separation. The mother liquor enters a solvent recovery system for recycling, a filter cake is left in a centrifuge, and a prepared water phase is leached;
④ rinsing with water phase
③, washing the filter cake in the centrifuge with deionized water or room-temperature water washing filtrate generated in ⑤, centrifuging, spin-drying, washing the filter cake with room-temperature water, sending water-phase washing filtrate generated in the water-phase washing process into a water-phase washing filtrate storage tank, and replacing the deionized water in the first step ① heating treatment process of the production batch after preparation;
⑤ washing with water at room temperature, and centrifuging
Preparing a filter cake from ④, preparing slurry by using deionized water, feeding the slurry into a room temperature water washing tank, wherein the deionized water accounts for 70-120% of the mass of acetic acid used in the dissolving and decoloring steps in the first step, stirring and washing for 30 minutes in the water washing tank, performing centrifugal filtration, performing solid-liquid separation, drying the filter cake, feeding room temperature water washing filtrate into a room temperature water washing filtrate storage tank, and rinsing ④ aqueous phases in a prepared batch to replace the deionized water for recycling;
⑥ drying
Washing the product with ⑤ items of room temperature water, drying the filter cake after centrifugation by a double-cone vacuum dryer to obtain the mixed long carbon chain dibasic acid product, wherein the product quality reaches the following technical indexes:
in the preparation method of the high-purity mixed long-carbon-chain dicarboxylic acid, the short-carbon-chain mixed acid impurities are removed through the technical steps of elutriation extraction and standing layering. The method solves the technical problems of high impurity content, low product purity and high chroma of the long carbon chain mixed dicarboxylic acid product in the prior art, and is a technical characteristic contributing to the completion of the task of the invention.
The principle of the water-out extraction step of the invention is based on that firstly, the acetic acids with different water contents have different solubilities on the dibasic acid, the higher the water content is, the lower the solubility of the dibasic acid in the acetic acids is, and the solubility of the dilute acetic acid on the dibasic acid is greatly reduced in the water content range of the water-out extraction step, so that the dibasic acid is separated out from the original rectification heavy component liquid;
in addition, the dibasic acids with different carbon chain lengths have different melting points, C10～C18The melting points of the dicarboxylic acids are all above 100 ℃ and C9The melting point of the following dicarboxylic acid is lower, and the short-chain dicarboxylic acid with low melting point gradually reaches the melting point in the temperature rising process of the water-out extraction of the inventionMelting point and is in a molten state, and the density is higher, so the solvent is separated from the mixed solvent of acetic acid and water and gradually settles to the bottom of the phase separation tank. But also a clear layered interface with the solvent. And the water is discharged by opening a valve arranged at the bottom of the phase separation tank. The impurity of the short carbon chain mixed dicarboxylic acid is easily removed.
Moreover, the problem of acetic acid gas loss and the problem of long drying period in the natural drying process are overcome, the acetic acid in the rectification heavy component is effectively recovered, the purity of the long carbon chain dibasic acid in the rectification heavy component is improved, and the three purposes are achieved: economic, environment-friendly and high in purity.
According to the preparation method of the high-purity mixed long-carbon-chain dicarboxylic acid, ① refined dissolving and decoloring sections of the mixed long-carbon-chain dicarboxylic acid are used, acetic acid is used as a solvent, a elutriation crystallization filter cake is heated and dissolved, and activated carbon is used for adsorbing and decoloring the dissolved solution.
The preparation method of the high-purity mixed long carbon chain dicarboxylic acid comprises the following operation steps:
first step of removing short carbon chain mixed acid impurities
① extraction by water extraction
And (2) putting the heavy component material into a phase separation tank provided with a temperature control device, and adding deionized water, wherein the adding amount is controlled in a range from the weight of the heavy component material to the weight of 1: 1.0-1: 2.5 is between; heating to 70-90 ℃ under stirring, carrying out elutriation extraction for 1.5-2 hours at the temperature of 70-90 ℃, extracting the mixed long-carbon-chain dibasic acid into a mixed solvent of acetic acid and water, and simultaneously melting impurities of the short-carbon-chain mixed acid to be in a molten state;
② standing for layering
Standing for 1.5-2 hours at the temperature of 70-90 ℃ under heat preservation until materials are layered, wherein the upper layer is an acetic acid and water mixed solvent extract of mixed long carbon chain dicarboxylic acid, and the lower layer is short carbon chain mixed acid melt impurities with a low melting point and carbon atom number less than or equal to 9;
③ removal of short carbon chain mixed acid impurities
Discharging ② layered impurities of the low-melting-point short-carbon-chain mixed acid melt with the carbon number less than or equal to 9 at the lower layer from the bottom of the layering tank, collecting, and performing post-treatment;
second step preparation of mixed long carbon chain dibasic acid crude product
① cooling crystallization
Slowly cooling the acetic acid and water mixed solvent extract of the mixed long carbon chain dibasic acid from which the impurities are removed in the first step to be less than or equal to 30 ℃ in a crystallization kettle under stirring, so that the mixed long carbon chain dibasic acid is crystallized and separated out;
② filtration and separation
Filtering and separating materials from item ① by a plate-and-frame filter press, and removing filtered mother liquor into a solvent recovery system, wherein a filter cake is a crude product of the mixed long-carbon chain dicarboxylic acid;
the third step is the refining of the mixed long carbon chain dibasic acid
① dissolving and decolorizing
a. Dissolution
And (3) putting the mixed long carbon chain dibasic acid crude product prepared in the second step into a dissolving and decoloring reaction kettle, and mixing the mixed long carbon chain dibasic acid crude product with the following components in percentage by weight: acetic acid wt ═ 1: 1.0-1: 2.0, adding acetic acid, stirring, heating to 80-95 ℃, keeping the temperature and dissolving completely, and waiting for decolorization;
b. decolorizing and filtering
And (b) adding activated carbon into the material dissolved in the item a in a decoloring kettle, wherein the adding amount is controlled in a way that the mass ratio of the crude product to the activated carbon is 1: 0.05-1: between 0.1; stirring, keeping the temperature and decoloring for 0.5-2 hours, then filtering by using a plate-and-frame filter press, and transferring filtrate into a crystallizing tank for crystallization;
② cooling crystallization
Naturally cooling the filtrate after the decolorization treatment to 50-75 ℃ under stirring in a crystallizing tank; then, gradually opening a circulating cooling water valve to reduce the temperature of the materials in the crystallizing tank to be less than or equal to 30 ℃ until the crystallization is complete;
③ centrifuging and separating
And (5) putting the materials in the crystallization tank into a centrifugal machine for solid-liquid separation. The mother liquor enters a solvent recovery system for recycling, a filter cake is left in a centrifuge, and a prepared water phase is leached;
④ rinsing with water phase
③, washing the filter cake in the centrifuge with deionized water or room-temperature water washing filtrate generated in ⑤, centrifuging, spin-drying, washing the filter cake with room-temperature water, sending water-phase washing filtrate generated in the water-phase washing process into a water-phase washing filtrate storage tank, and replacing the deionized water in the first step ① heating treatment process of the production batch after preparation;
⑤ washing with water at room temperature, and centrifuging
Preparing a filter cake from ④, preparing slurry by using deionized water, feeding the slurry into a room temperature water washing tank, wherein the deionized water accounts for 70-120% of the mass of acetic acid used in the dissolving and decoloring steps in the first step, stirring and washing for 30 minutes in the water washing tank, performing centrifugal filtration, performing solid-liquid separation, drying the filter cake, feeding room temperature water washing filtrate into a room temperature water washing filtrate storage tank, and rinsing ④ aqueous phases in a prepared batch to replace the deionized water for recycling;
⑥ drying
Washing the product with ⑤ items of room temperature water, drying the filter cake after centrifugation by a double-cone vacuum dryer to obtain the mixed long carbon chain dibasic acid product, wherein the product quality reaches the following technical indexes:
is a preferable technical proposal.
The preparation method of the high-purity mixed long carbon chain dicarboxylic acid comprises the following operation steps:
first step of removing short carbon chain mixed acid impurities
① extraction by water extraction
And (3) putting the heavy component material into a phase separation tank provided with a temperature control device, and adding deionized water, wherein the adding amount is controlled to be equal to the weight of the heavy component material wt: 1: 2.0; heating to 85 ℃ under stirring, carrying out elutriation extraction for 2 hours at the temperature of 85 ℃, extracting the mixed long-carbon-chain dibasic acid into a mixed solvent of acetic acid and water, and simultaneously melting impurities of the short-carbon-chain mixed acid to be in a molten state;
② standing for layering
Standing for 1.5-2 hours at the temperature of 85 ℃ under the condition of heat preservation until materials are layered, wherein the upper layer is an acetic acid and water mixed solvent extract of mixed long carbon chain dicarboxylic acid, and the lower layer is short carbon chain mixed acid melt impurities with a low melting point and carbon atom number less than or equal to 9;
③ removal of short carbon chain mixed acid impurities
Discharging ② layered impurities of the low-melting-point short-carbon-chain mixed acid melt with the carbon number less than or equal to 9 at the lower layer from the bottom of the layering tank, collecting, and performing post-treatment;
second step preparation of mixed long carbon chain dibasic acid crude product
① cooling crystallization
Slowly cooling the acetic acid and water mixed solvent extract of the mixed long carbon chain dibasic acid from which the impurities are removed in the first step to be less than or equal to 30 ℃ in a crystallization kettle under stirring, so that the mixed long carbon chain dibasic acid is crystallized and separated out;
② filtration and separation
Filtering and separating materials from item ① by a plate-and-frame filter press, and removing filtered mother liquor into a solvent recovery system, wherein a filter cake is a crude product of the mixed long-carbon chain dicarboxylic acid;
the third step is the refining of the mixed long carbon chain dibasic acid
① dissolving and decolorizing
a. Dissolution
And (3) putting the mixed long carbon chain dibasic acid crude product prepared in the second step into a dissolving and decoloring reaction kettle, and mixing the mixed long carbon chain dibasic acid crude product with the following components in percentage by weight: acetic acid wt ═ 1: 2.0, adding acetic acid, stirring, heating to 95 ℃, keeping the temperature and dissolving completely for decolorization;
b. decolorizing and filtering
And (b) adding activated carbon into the material dissolved in the item a in a decoloring kettle, wherein the adding amount is controlled in a mass ratio of 1: 0.05; stirring, keeping the temperature and decoloring for 1.5 hours, filtering by a plate-and-frame filter press, and transferring filtrate into a crystallizing tank for crystallization;
② cooling crystallization
Naturally cooling the decolorized filtrate to 50-70 ℃ under stirring in a crystallizing tank; then, gradually opening a circulating cooling water valve to reduce the temperature of the materials in the crystallizing tank to be less than or equal to 30 ℃ until the crystallization is complete;
③ centrifuging and separating
And after the temperature of the crystallizing tank is reduced to be less than or equal to 30 ℃, putting the materials in the crystallizing tank into a centrifugal machine for solid-liquid separation. The mother liquor enters a solvent recovery system for recycling, a filter cake is left in a centrifuge, and a prepared water phase is leached;
④ rinsing with water phase
③, washing the filter cake in the centrifuge with deionized water or room-temperature water washing filtrate generated in ⑤, centrifuging, spin-drying, washing the filter cake with room-temperature water, sending water-phase washing filtrate generated in the water-phase washing process into a water-phase washing filtrate storage tank, and replacing the deionized water in the first step ① heating treatment process of the production batch after preparation;
⑤ washing with water at room temperature, and centrifuging
Preparing a filter cake from ④, preparing slurry by using deionized water, feeding the slurry into a room temperature water washing tank, wherein the deionized water accounts for 70-120% of the mass of acetic acid used in the dissolving and decoloring steps in the first step, stirring and washing for 30 minutes in the water washing tank, performing centrifugal filtration, performing solid-liquid separation, drying the filter cake, feeding room temperature water washing filtrate into a room temperature water washing filtrate storage tank, and rinsing ④ aqueous phases in a prepared batch to replace the deionized water for recycling;
⑥ drying
Washing the product with ⑤ items of room temperature water, drying the filter cake after centrifugation by a double-cone vacuum dryer to obtain the mixed long carbon chain dibasic acid product, wherein the product quality reaches the following technical indexes:
is an optimal technical scheme.
The application of the high-purity mixed long carbon chain dicarboxylic acid is suitable for being used as a surfactant, an environment-friendly high-performance semisynthetic cutting fluid, high-grade lubricating oil and artificially synthesized inferior incense.
Compared with the prior art, the technical scheme disclosed by the high-purity mixed long carbon chain dicarboxylic acid and the preparation method thereof can produce the following positive effects:
1. provides a mixed long carbon chain dicarboxylic acid product which has high purity and good color and can meet the requirements of synthesizing industrial products such as dibasic acid salt surfactant, alcohol amine salt antirust and wear-resistant agent, artificially synthesized joss stick and the like as synthesis raw materials.
2, the preparation method of the mixed long carbon chain dicarboxylic acid has the advantages of high yield, low cost, resource saving and environmental protection.
3. The defects that solvent resources are wasted, precious land is occupied, and the atmosphere and water environment are polluted by a natural airing method in the prior art are overcome.
4. Provides a process method for removing short-carbon-chain mixed dicarboxylic acid with less than 9 carbon atoms, which is a main impurity in a mixed long-carbon-chain dicarboxylic acid product.
5. The quality of the mixed long carbon chain dicarboxylic acid product prepared by the method of the invention reaches the following technical indexes:
Detailed Description
The invention will be further described in detail with reference to the following examples:
embodiment 1 a method for preparing a mixed long carbon chain dicarboxylic acid with high purity according to the present invention is a method for preparing a heavy component material by using a heavy component material obtained by recycling acetic acid as a solvent from a recrystallization filtered mother liquor generated in a recrystallization refining process of an industrial dodecyl dicarboxylic acid.
The method comprises the following operation steps:
first step of removing short carbon chain mixed acid impurities
① extraction by water extraction
Putting 2000kg of heavy component material with the mixed dicarboxylic acid content of 320g/L and the acetic acid content of 68 wt% and 6000L of deionized water into a phase separation tank with a temperature control device, stirring, heating to 90 ℃, stirring, carrying out heat preservation and water precipitation extraction for 1 hour, extracting the mixed long carbon chain dicarboxylic acid into a mixed solvent of acetic acid and water, and simultaneously melting impurities of the short carbon chain mixed acid to be in a molten state;
② standing for layering
Keeping the temperature and standing for 2 hours at the temperature of 90 ℃ until the materials are layered, wherein the upper layer is the mixed solvent extract of acetic acid and water mixed with long carbon chain dicarboxylic acid, and the lower layer is the short carbon chain mixed acid melt impurity with the low melting point and the carbon atom number less than or equal to 9.
③ removal of short carbon chain mixed acid impurities
Discharging ② layered short carbon chain mixed acid melt impurities with the lower layer and the low melting point, the number of carbon atoms being less than or equal to 9 from the bottom of the phase separation tank, collecting 80L of short carbon chain mixed acid melt impurities for post-treatment, mixing acetic acid and water mixed solvent extract of long carbon chain dicarboxylic acid at the upper layer, transferring the mixed solvent extract into a crystallization kettle, and cooling and crystallizing;
second step preparation of mixed long carbon chain dibasic acid crude product
① cooling crystallization
Slowly cooling the acetic acid and water mixed solvent extract of the mixed long carbon chain dibasic acid from which the impurities are removed in the first step to be less than or equal to 30 ℃ in a crystallization kettle under stirring, so that the mixed long carbon chain dibasic acid is crystallized and separated out;
② filtration and separation
Filtering and separating materials from ① items by a plate-and-frame filter press, and removing filtered mother liquor into a solvent recovery system, wherein a filter cake is 545Kg of crude mixed long carbon chain dicarboxylic acid;
the third step is the refining of the mixed long carbon chain dibasic acid
① dissolving and decolorizing
a. Dissolution
Putting the mixed long carbon chain dibasic acid crude product prepared in the second step into a dissolving and decoloring reaction kettle, and adding 1500Kg of acetic acid with the content of more than or equal to 99 percent. Heating to 90 ℃ under stirring, preserving heat and dissolving for decoloring;
b. decolorizing and filtering
Adding 50Kg of activated carbon into the material dissolved in the item a in a decoloring kettle, stirring, keeping the temperature and decoloring for 1 hour, filtering by a plate-and-frame filter press, and transferring the filtrate into a crystallizing tank for crystallization;
② cooling crystallization
Stirring in a crystallizing tank, and naturally cooling the decolorized filtrate to 69 ℃; then, gradually opening a cooling circulating water valve, controlling the cooling speed from slow to fast, cooling and crystallizing until the temperature is reduced to be less than or equal to 30 ℃; the whole cooling process is controlled for 6-8 hours.
③ centrifuging and separating
And after the temperature of the crystallizing tank is reduced to be less than or equal to 30 ℃, putting the materials in the crystallizing tank into a centrifugal machine for solid-liquid separation. The mother liquor enters a solvent recovery system for recycling, a filter cake is left in a centrifuge, and a prepared water phase is leached;
④ rinsing with water phase
In the ③ phase, 200L of deionized water is used for leaching filter cakes in the centrifuge, the filter cakes are centrifuged and dried for 30 minutes again, the filter cakes are washed with water at room temperature, water-phase leaching filtrate generated in the water-phase leaching process is sent into a water-phase leaching filtrate storage tank, and the filter cakes are used for replacing the deionized water in the subsequent first step ① heating treatment process of a production batch;
⑤ washing with water at room temperature, and centrifuging
Preparing a filter cake from ④, preparing slurry by using deionized water, feeding the slurry into a room temperature water washing tank, adding 2000L of deionized water, stirring and washing for 30 minutes, performing centrifugal filtration, performing solid-liquid separation, and drying the filter cake, wherein room temperature water washing filtrate is fed into a room temperature water washing filtrate storage tank, preparing ④ aqueous phases for leaching, replacing the deionized water, and recycling;
⑥ drying
Washing the product with ⑤ items of room temperature water, drying the filter cake after centrifugation by a double-cone vacuum dryer to obtain 470Kg of mixed long carbon chain dibasic acid product, wherein the product quality reaches the following technical indexes:
embodiment 2 a method for preparing a mixed long carbon chain dicarboxylic acid with high purity according to the present invention, the heavy component material is prepared by using a recrystallization filtered mother liquor generated in a recrystallization refining process of an industrial undecyl dicarboxylic acid, and recovering acetic acid as a solvent.
The method comprises the following operation steps:
first step of removing short carbon chain mixed acid impurities
① extraction by water extraction
Putting 2500kg of heavy component material with the mixed dicarboxylic acid content of 330g/L and the acetic acid content of 67 wt% and 2500L of deionized water into a phase separation tank with a temperature control device, stirring, heating to 98 ℃, stirring, performing heat preservation and water precipitation extraction for 1.5 hours, extracting the mixed long carbon chain dicarboxylic acid into a mixed solvent of acetic acid and water, and simultaneously melting impurities of the short carbon chain mixed acid to be in a molten state;
② standing for layering
Keeping the temperature and standing for 1 hour at the temperature of 90 ℃ until the materials are layered, wherein the upper layer is the mixed solvent extract of acetic acid and water mixed with long carbon chain dicarboxylic acid, and the lower layer is the short carbon chain mixed acid melt impurity with the low melting point and the carbon atom number less than or equal to 9.
③ removal of short carbon chain mixed acid impurities
Discharging ② layered short carbon chain mixed acid melt impurities with the lower layer and the low melting point, the number of carbon atoms being less than or equal to 9 from the bottom of the phase separation tank, collecting 120L of short carbon chain mixed acid melt impurities for post-treatment, mixing acetic acid and water mixed solvent extract of long carbon chain dicarboxylic acid at the upper layer, transferring the mixed solvent extract into a crystallization kettle, and cooling and crystallizing;
second step preparation of mixed long carbon chain dibasic acid crude product
① cooling crystallization
Slowly cooling the acetic acid and water mixed solvent extract of the mixed long carbon chain dibasic acid from which the impurities are removed in the first step to be less than or equal to 30 ℃ in a crystallization kettle under stirring, so that the mixed long carbon chain dibasic acid is crystallized and separated out;
② filtration and separation
Filtering and separating materials from ① items by a plate-and-frame filter press, and removing filtered mother liquor into a solvent recovery system, wherein the filter cake is 765Kg of crude mixed long carbon chain dicarboxylic acid;
the third step is the refining of the mixed long carbon chain dibasic acid
① dissolving and decolorizing
a. Dissolution
Putting the mixed long carbon chain dibasic acid crude product prepared in the second step into a dissolving and decoloring reaction kettle, and adding 1500Kg of acetic acid with the content of more than or equal to 99 percent. Heating to 98 deg.C under stirring, maintaining the temperature for dissolving, and decolorizing;
b. decolorizing and filtering
Adding 50Kg of activated carbon into the material dissolved in the item a in a decoloring kettle, stirring, keeping the temperature and decoloring for 0.5 (0.5-2) hour, then filtering by a plate-and-frame filter press, transferring the filtrate into a crystallizing tank for crystallization;
② cooling crystallization
Stirring in a crystallizing tank, and naturally cooling the decolorized filtrate to 72 ℃; then, gradually opening a cooling circulating water valve, controlling the cooling speed from slow to fast, cooling and crystallizing until the temperature is reduced to be less than or equal to 30 ℃; the whole cooling process is controlled for 6-8 hours.
③ centrifuging and separating
And after the temperature of the crystallizing tank is reduced to be less than or equal to 30 ℃, putting the materials in the crystallizing tank into a centrifugal machine for solid-liquid separation. The mother liquor enters a solvent recovery system for recycling, a filter cake is left in a centrifuge, and a prepared water phase is leached;
④ rinsing with water phase
In the ③ phase, 200L of deionized water is used for leaching filter cakes in the centrifuge, the filter cakes are centrifuged and dried for 30 minutes again, the filter cakes are washed with water at room temperature, water-phase leaching filtrate generated in the water-phase leaching process is sent into a water-phase leaching filtrate storage tank, and the filter cakes are used for replacing the deionized water in the subsequent first step ① heating treatment process of a production batch;
⑤ washing with water at room temperature, and centrifuging
Preparing a filter cake from ④ by using deionized water, then sending the filter cake into a room-temperature water washing tank, adding 2000L of deionized water into the water washing tank, stirring and washing for 30 minutes, carrying out centrifugal filtration, carrying out solid-liquid separation, and drying the filter cake;
⑥ drying
The ⑤ items of room temperature water washing are carried out, the filter cake after centrifugation is dried by a double-cone vacuum dryer, and 565Kg of mixed long carbon chain dibasic acid product is obtained, wherein the product quality reaches the following technical indexes:
embodiment 3 a method for preparing a mixed long carbon chain dicarboxylic acid with high purity according to the present invention, the heavy component material is prepared by using a recrystallization filtered mother liquor generated during a recrystallization refining process of an industrial tridecane dicarboxylic acid, and recovering acetic acid as a solvent.
The method comprises the following operation steps:
first step of removing short carbon chain mixed acid impurities
① extraction by water extraction
Putting 2000kg of heavy component material with the mixed dicarboxylic acid content of 310g/L and the acetic acid content of 69 wt% and 6000L of deionized water into a phase separation tank with a temperature control device, stirring, heating to 70 ℃, stirring, performing heat preservation and water precipitation extraction for 2 (1-2) hours, extracting the mixed long carbon chain dicarboxylic acid into a mixed solvent of acetic acid and water, and simultaneously melting impurities of the short carbon chain mixed acid to be in a molten state;
② standing for layering
Keeping the temperature and standing for 2 hours at the temperature of 70 ℃ until the materials are layered, wherein the upper layer is the mixed solvent extract of acetic acid and water mixed with long carbon chain dicarboxylic acid, and the lower layer is the short carbon chain mixed acid melt impurity with the low melting point and the carbon atom number less than or equal to 9.
③ removal of short carbon chain mixed acid impurities
Discharging ② layered short carbon chain mixed acid melt impurities with the lower layer and the low melting point, the number of carbon atoms being less than or equal to 9 from the bottom of the phase separation tank, collecting 85L short carbon chain mixed acid melt impurities for post-treatment, mixing acetic acid and water mixed solvent extract of long carbon chain dicarboxylic acid at the upper layer, transferring the mixed solvent extract into a crystallization kettle, and cooling and crystallizing;
second step preparation of mixed long carbon chain dibasic acid crude product
① cooling crystallization
Slowly cooling the acetic acid and water mixed solvent extract of the mixed long carbon chain dibasic acid from which the impurities are removed in the first step to be less than or equal to 30 ℃ in a crystallization kettle under stirring, so that the mixed long carbon chain dibasic acid is crystallized and separated out;
② filtration and separation
Filtering and separating materials from ① items by a plate-and-frame filter press, and removing filtered mother liquor into a solvent recovery system, wherein a filter cake is 655Kg of crude mixed long carbon chain dicarboxylic acid;
the third step is the refining of the mixed long carbon chain dibasic acid
① dissolving and decolorizing
a. Dissolution
Putting the mixed long carbon chain dibasic acid crude product prepared in the second step into a dissolving and decoloring reaction kettle, and adding 1500Kg of acetic acid with the content of more than or equal to 99 percent. Heating to 80 ℃ under stirring, preserving heat and dissolving for decoloring;
b. decolorizing and filtering
Adding 50Kg of activated carbon into the material dissolved in the item a in a decoloring kettle, decoloring for 2 (0.5-2) hours under stirring, filtering by a plate-and-frame filter press, and transferring the filtrate into a crystallizing tank for crystallization;
② cooling crystallization
Stirring in a crystallizing tank, and naturally cooling the decolorized filtrate to 70 ℃; then, gradually opening a cooling circulating water valve, controlling the cooling speed from slow to fast, cooling and crystallizing until the temperature is reduced to be less than or equal to 30 ℃; the whole cooling process is controlled for 6-8 hours.
③ centrifuging and separating
And after the temperature of the crystallizing tank is reduced to be less than or equal to 30 ℃, putting the materials in the crystallizing tank into a centrifugal machine for solid-liquid separation. The mother liquor enters a solvent recovery system for recycling, a filter cake is left in a centrifuge, and a prepared water phase is leached;
④ rinsing with water phase
In the ③ phase, 200L of deionized water is used for leaching filter cakes in the centrifuge, the filter cakes are centrifuged and dried for 30 minutes again, the filter cakes are washed with water at room temperature, water-phase leaching filtrate generated in the water-phase leaching process is sent into a water-phase leaching filtrate storage tank, and the filter cakes are used for replacing the deionized water in the subsequent first step ① heating treatment process of a production batch;
⑤ washing with water at room temperature, and centrifuging
Preparing a filter cake from ④ by using deionized water, then sending the filter cake into a room-temperature water washing tank, adding 2000L of deionized water into the water washing tank, stirring and washing for 30 minutes, carrying out centrifugal filtration, carrying out solid-liquid separation, and drying the filter cake;
⑥ drying
Washing the filter cake with ⑤ items of room temperature water, drying the filter cake after centrifugation by a double-cone vacuum dryer to obtain 460Kg of mixed long carbon chain dibasic acid product, wherein the product quality reaches the following technical indexes:
embodiment 4 a method for preparing a mixed long carbon chain dicarboxylic acid with high purity according to the present invention is provided, which is characterized in that a heavy component material obtained by recovering acetic acid as a solvent from a recrystallization filtered mother liquor generated in a recrystallization refining process of industrial tetradecyl dicarboxylic acid is used as a raw material.
The method comprises the following operation steps:
first step of removing short carbon chain mixed acid impurities
① extraction by water extraction
Putting 1500kg of heavy component material with the mixed dicarboxylic acid content of 310g/L and the acetic acid content of 69 wt% and 5000L of deionized water into a phase separation tank with a temperature control device, stirring, heating to 80 ℃, stirring, performing heat preservation and water precipitation extraction for 1.6 hours, extracting the mixed long carbon chain dicarboxylic acid into a mixed solvent of acetic acid and water, and simultaneously melting impurities of the short carbon chain mixed acid to be in a molten state;
② standing for layering
Standing at 80 deg.C for 1.5 hr until materials are separated, the upper layer is mixed with acetic acid and water mixed solvent extract of long carbon chain dicarboxylic acid, and the lower layer is short carbon chain mixed acid melt impurity with low melting point and carbon atom number less than or equal to 9.
③ removal of short carbon chain mixed acid impurities
Discharging ② layered short carbon chain mixed acid melt impurities with the lower layer and the low melting point, the number of carbon atoms being less than or equal to 9 from the bottom of the phase separation tank, collecting 55L short carbon chain mixed acid melt impurities, carrying out post-treatment, mixing the acetic acid and water mixed solvent extract of the long carbon chain dicarboxylic acid on the upper layer, transferring the mixture into a crystallization kettle, and carrying out cooling crystallization;
second step preparation of mixed long carbon chain dibasic acid crude product
① cooling crystallization
Slowly cooling the acetic acid and water mixed solvent extract of the mixed long carbon chain dibasic acid from which the impurities are removed in the first step to be less than or equal to 30 ℃ in a crystallization kettle under stirring, so that the mixed long carbon chain dibasic acid is crystallized and separated out;
② filtration and separation
The materials from ① are filtered and separated by a plate-and-frame filter press, and filtered mother liquor is sent to a solvent recovery system, wherein the filter cake is 512Kg of crude mixed long carbon chain dicarboxylic acid;
the third step is the refining of the mixed long carbon chain dibasic acid
① dissolving and decolorizing
a. Dissolution
Putting the mixed long carbon chain dibasic acid crude product prepared in the second step into a dissolving and decoloring reaction kettle, and adding 1500Kg of acetic acid with the content of more than or equal to 99 percent. Heating to 85 deg.C under stirring, maintaining the temperature for dissolving, and decolorizing;
b. decolorizing and filtering
Adding 50Kg of activated carbon into the material dissolved in the item a in a decoloring kettle, stirring, keeping the temperature and decoloring for 1.5 hours, then filtering by a plate-and-frame filter press, transferring the filtrate into a crystallizing tank for crystallization;
② cooling crystallization
Stirring in a crystallizing tank, and naturally cooling the decolorized filtrate to 71 ℃; then, gradually opening a cooling circulating water valve, controlling the cooling speed from slow to fast, cooling and crystallizing until the temperature is reduced to be less than or equal to 30 ℃; the whole cooling process is controlled for 6-8 hours.
③ centrifuging and separating
And after the temperature of the crystallizing tank is reduced to be less than or equal to 30 ℃, putting the materials in the crystallizing tank into a centrifugal machine for solid-liquid separation. The mother liquor enters a solvent recovery system for recycling, a filter cake is left in a centrifuge, and a prepared water phase is leached;
④ rinsing with water phase
In the ③ phase, 200L of deionized water is used for leaching filter cakes in the centrifuge, the filter cakes are centrifuged and dried for 30 minutes again, the filter cakes are washed with water at room temperature, water-phase leaching filtrate generated in the water-phase leaching process is sent into a water-phase leaching filtrate storage tank, and the filter cakes are used for replacing the deionized water in the subsequent first step ① heating treatment process of a production batch;
⑤ washing with water at room temperature, and centrifuging
Preparing a filter cake from ④ by using deionized water, then sending the filter cake into a room-temperature water washing tank, adding 2000L of deionized water into the water washing tank, stirring and washing for 30 minutes, carrying out centrifugal filtration, carrying out solid-liquid separation, and drying the filter cake;
⑥ drying
Washing the product with ⑤ items of room temperature water, drying the filter cake after centrifugation by a double-cone vacuum dryer to obtain 360Kg of mixed long carbon chain dibasic acid product, wherein the product quality reaches the following technical indexes:
Claims (6)
1. a high-purity mixed long-carbon-chain dicarboxylic acid is prepared by taking heavy component materials as raw materials, wherein heavy component materials are obtained by recycling solvent acetic acid from recrystallization filtered mother liquor generated in the recrystallization refining process of industrial long-carbon-chain dicarboxylic acid; the method is characterized by comprising the following steps of firstly adding deionized water into the heavy component material raw materials, heating while stirring, extracting mixed long carbon chain dicarboxylic acid into a solution, standing for layering, and removing impurities of short carbon chain mixed acid with a lower layer in a molten state; then, cooling the upper layer extracting solution, crystallizing and filtering to obtain a crude product; recrystallizing, refining and purifying the obtained crude product to obtain high-purity mixed long carbon chain dicarboxylic acid; the product quality reaches the following technical indexes:
2. high purity mixed long carbon chain dicarboxylic acids according to claim 1, characterized in that the heavy component material is C11～C18In the refining and purifying process of the long carbon chain dicarboxylic acid, generated recrystallization filtration mother liquor is subjected to solvent acetic acid recovery, and heavy components are left at the bottom of the distillation still.
3. The method for preparing a mixed long carbon chain dicarboxylic acid of high purity according to claim 1, comprising the steps of:
first step of removing short carbon chain mixed acid impurities
① extraction by water extraction
And (3) putting the heavy component material into a phase separation tank provided with a temperature control device, adding deionized water, and controlling the adding amount to be equal to the weight of the heavy component material: deionized water wr ═ 1: 0.5-1: 3.5 is between; heating to 70-98 ℃ under stirring, carrying out elutriation and extraction for 1-2 hours at the temperature of 70-98 ℃, extracting the mixed long-carbon-chain dibasic acid into an acetic acid and water mixed solvent, and simultaneously melting impurities of the short-carbon-chain mixed acid to be in a molten state;
② standing for layering
Standing for 1-2 hours at the temperature of 70-98 ℃ under heat preservation until materials are layered, wherein the upper layer is an acetic acid and water mixed solvent extract of mixed long carbon chain dicarboxylic acid, and the lower layer is short carbon chain mixed acid melt impurities with a low melting point and carbon atom number less than or equal to 9;
③ removal of short carbon chain mixed acid impurities
Discharging ② layered impurities of the low-melting-point short-carbon-chain mixed acid melt with the carbon number less than or equal to 9 at the lower layer from the bottom of the layering tank, collecting, and performing post-treatment;
second step preparation of mixed long carbon chain dibasic acid crude product
① cooling crystallization
Slowly cooling the acetic acid and water mixed solvent extract of the mixed long carbon chain dibasic acid from which the impurities are removed in the first step to be less than or equal to 30 ℃ in a crystallization kettle under stirring, so that the mixed long carbon chain dibasic acid is crystallized and separated out;
② filtration and separation
Filtering and separating materials from item ① by a plate-and-frame filter press, and removing filtered mother liquor into a solvent recovery system, wherein a filter cake is a crude product of the mixed long-carbon chain dicarboxylic acid;
the third step is the refining of the mixed long carbon chain dibasic acid
① dissolving and decolorizing
a. Dissolution
And (3) putting the mixed long carbon chain dibasic acid crude product prepared in the second step into a dissolving and decoloring reaction kettle, and mixing the mixed long carbon chain dibasic acid crude product with the following components in percentage by weight: acetic acid wt ═ 1: 0.8-1: 3.0, adding acetic acid, stirring, heating to 80-100 ℃, keeping the temperature and dissolving completely for decolorization;
b. decolorizing and filtering
And (b) adding activated carbon into the material dissolved in the item a in a decoloring kettle, wherein the adding amount is controlled in a way that the mass ratio of the crude product to the activated carbon is 1: 0.05-1: between 0.1; stirring, keeping the temperature and decoloring for 0.5-2 hours, then filtering by using a plate-and-frame filter press, and transferring filtrate into a crystallizing tank for crystallization;
② crystallizing by cooling
Naturally cooling the filtrate after the decolorization treatment to 50-75 ℃ under stirring in a crystallizing tank; then, gradually opening a circulating cooling water valve to reduce the temperature of the materials in the crystallizing tank to be less than or equal to 30 ℃ until the crystallization is complete;
③ centrifuging and separating
And (5) putting the materials in the crystallization tank into a centrifugal machine for solid-liquid separation. The mother liquor enters a solvent recovery system for recycling, a filter cake is left in a centrifuge, and a prepared water phase is leached;
④ rinsing with water phase
③, washing the filter cake in the centrifuge with deionized water or room-temperature water washing filtrate generated in ⑤, centrifuging, spin-drying, washing the filter cake with room-temperature water, sending water-phase washing filtrate generated in the water-phase washing process into a water-phase washing filtrate storage tank, and replacing the deionized water in the first step ① heating treatment process of the production batch after preparation;
⑤ washing with water at room temperature, and centrifuging
Preparing a filter cake from ④, preparing slurry by using deionized water, feeding the slurry into a room temperature water washing tank, wherein the deionized water accounts for 70-120% of the mass of acetic acid used in the dissolving and decoloring steps in the first step, stirring and washing for 30 minutes in the water washing tank, performing centrifugal filtration, performing solid-liquid separation, drying the filter cake, feeding room temperature water washing filtrate into a room temperature water washing filtrate storage tank, and rinsing ④ aqueous phases in a prepared batch to replace the deionized water for recycling;
⑥ drying
Washing the product with ⑤ items of room temperature water, drying the filter cake after centrifugation by a double-cone vacuum dryer to obtain the mixed long carbon chain dibasic acid product, wherein the product quality reaches the following technical indexes:
4. the method for preparing a mixed long carbon chain dicarboxylic acid of high purity according to claim 1, comprising the steps of:
first step of removing short carbon chain mixed acid impurities
① extraction by water extraction
And (2) putting the heavy component material into a phase separation tank provided with a temperature control device, and adding deionized water, wherein the adding amount is controlled in a range from the weight of the heavy component material to the weight of 1: 1.0-1: 2.5 is between; heating to 70-90 ℃ under stirring, carrying out elutriation extraction for 1.5-2 hours at the temperature of 70-90 ℃, extracting the mixed long-carbon-chain dibasic acid into a mixed solvent of acetic acid and water, and simultaneously melting impurities of the short-carbon-chain mixed acid to be in a molten state;
② standing for layering
Standing for 1.5-2 hours at the temperature of 70-90 ℃ under heat preservation until materials are layered, wherein the upper layer is an acetic acid and water mixed solvent extract of mixed long carbon chain dicarboxylic acid, and the lower layer is short carbon chain mixed acid melt impurities with a low melting point and carbon atom number less than or equal to 9;
③ removal of short carbon chain mixed acid impurities
Discharging ② layered impurities of the low-melting-point short-carbon-chain mixed acid melt with the carbon number less than or equal to 9 at the lower layer from the bottom of the layering tank, collecting, and performing post-treatment;
second step preparation of mixed long carbon chain dibasic acid crude product
① cooling crystallization
Slowly cooling the acetic acid and water mixed solvent extract of the mixed long carbon chain dibasic acid from which the impurities are removed in the first step to be less than or equal to 30 ℃ in a crystallization kettle under stirring, so that the mixed long carbon chain dibasic acid is crystallized and separated out;
② filtration and separation
Filtering and separating materials from item ① by a plate-and-frame filter press, and removing filtered mother liquor into a solvent recovery system, wherein a filter cake is a crude product of the mixed long-carbon chain dicarboxylic acid;
the third step is the refining of the mixed long carbon chain dibasic acid
① dissolving and decolorizing
a. Dissolution
And (3) putting the mixed long carbon chain dibasic acid crude product prepared in the second step into a dissolving and decoloring reaction kettle, and mixing the mixed long carbon chain dibasic acid crude product with the following components in percentage by weight: acetic acid wt ═ 1: 1.0-1: 2.0, adding acetic acid, stirring, heating to 80-95 ℃, keeping the temperature and dissolving completely, and waiting for decolorization;
b. decolorizing and filtering
And (b) adding activated carbon into the material dissolved in the item a in a decoloring kettle, wherein the adding amount is controlled in a way that the mass ratio of the crude product to the activated carbon is 1: 0.05-1: between 0.1; stirring, keeping the temperature and decoloring for 0.5-2 hours, then filtering by using a plate-and-frame filter press, and transferring filtrate into a crystallizing tank for crystallization;
② cooling crystallization
Naturally cooling the filtrate after the decolorization treatment to 50-75 ℃ under stirring in a crystallizing tank; then, gradually opening a circulating cooling water valve to reduce the temperature of the materials in the crystallizing tank to be less than or equal to 30 ℃ until the crystallization is complete;
③ centrifuging and separating
And (5) putting the materials in the crystallization tank into a centrifugal machine for solid-liquid separation. The mother liquor enters a solvent recovery system for recycling, a filter cake is left in a centrifuge, and a prepared water phase is leached;
④ rinsing with water phase
③, washing the filter cake in the centrifuge with deionized water or room-temperature water washing filtrate generated in ⑤, centrifuging, spin-drying, washing the filter cake with room-temperature water, sending water-phase washing filtrate generated in the water-phase washing process into a water-phase washing filtrate storage tank, and replacing the deionized water in the first step ① heating treatment process of the production batch after preparation;
⑤ washing with water at room temperature, and centrifuging
Preparing a filter cake from ④, preparing slurry by using deionized water, feeding the slurry into a room temperature water washing tank, wherein the deionized water accounts for 70-120% of the mass of acetic acid used in the dissolving and decoloring steps in the first step, stirring and washing for 30 minutes in the water washing tank, performing centrifugal filtration, performing solid-liquid separation, drying the filter cake, feeding room temperature water washing filtrate into a room temperature water washing filtrate storage tank, and rinsing ④ aqueous phases in a prepared batch to replace the deionized water for recycling;
⑥ drying
Washing the product with ⑤ items of room temperature water, drying the filter cake after centrifugation by a double-cone vacuum dryer to obtain the mixed long carbon chain dibasic acid product, wherein the product quality reaches the following technical indexes:
5. the method for preparing a mixed long carbon chain dicarboxylic acid of high purity according to claim 1, comprising the steps of:
first step of removing short carbon chain mixed acid impurities
① extraction by water extraction
And (2) putting the heavy component material into a phase separation tank provided with a temperature control device, adding deionized water, and controlling the adding amount to be equal to 1: 2.0; heating to 85 ℃ under stirring, carrying out elutriation extraction for 2 hours at the temperature of 85 ℃, extracting the mixed long-carbon-chain dibasic acid into a mixed solvent of acetic acid and water, and simultaneously melting impurities of the short-carbon-chain mixed acid to be in a molten state;
② standing for layering
Standing for 1.5-2 hours at the temperature of 85 ℃ under the condition of heat preservation until materials are layered, wherein the upper layer is an acetic acid and water mixed solvent extract of mixed long carbon chain dicarboxylic acid, and the lower layer is short carbon chain mixed acid melt impurities with a low melting point and carbon atom number less than or equal to 9;
③ removal of short carbon chain mixed acid impurities
Discharging ② layered impurities of the low-melting-point short-carbon-chain mixed acid melt with the carbon number less than or equal to 9 at the lower layer from the bottom of the layering tank, collecting, and performing post-treatment;
second step preparation of mixed long carbon chain dibasic acid crude product
① cooling crystallization
Slowly cooling the acetic acid and water mixed solvent extract of the mixed long carbon chain dibasic acid from which the impurities are removed in the first step to be less than or equal to 30 ℃ in a crystallization kettle under stirring, so that the mixed long carbon chain dibasic acid is crystallized and separated out;
② filtration and separation
Filtering and separating materials from item ① by a plate-and-frame filter press, and removing filtered mother liquor into a solvent recovery system, wherein a filter cake is a crude product of the mixed long-carbon chain dicarboxylic acid;
the third step is the refining of the mixed long carbon chain dibasic acid
① dissolving and decolorizing
a. Dissolution
And (3) putting the mixed long carbon chain dibasic acid crude product prepared in the second step into a dissolving and decoloring reaction kettle, and mixing the mixed long carbon chain dibasic acid crude product with the following components in percentage by weight: acetic acid wt ═ 1: 2.0, adding acetic acid, stirring, heating to 95 ℃, keeping the temperature and dissolving completely for decolorization;
b. decolorizing and filtering
And (b) adding activated carbon into the material dissolved in the item a in a decoloring kettle, wherein the adding amount is controlled in a mass ratio of 1: 0.05; stirring, keeping the temperature and decoloring for 1.5 hours, filtering by a plate-and-frame filter press, and transferring filtrate into a crystallizing tank for crystallization;
② cooling crystallization
Naturally cooling the decolorized filtrate to 50-70 ℃ under stirring in a crystallizing tank; then, gradually opening a circulating cooling water valve to reduce the temperature of the materials in the crystallizing tank to be less than or equal to 30 ℃ until the crystallization is complete;
③ centrifuging and separating
And after the temperature of the crystallizing tank is reduced to be less than or equal to 30 ℃, putting the materials in the crystallizing tank into a centrifugal machine for solid-liquid separation. The mother liquor enters a solvent recovery system for recycling, a filter cake is left in a centrifuge, and a prepared water phase is leached;
④ rinsing with water phase
③, washing the filter cake in the centrifuge with deionized water or room-temperature water washing filtrate generated in ⑤, centrifuging, spin-drying, washing the filter cake with room-temperature water, sending water-phase washing filtrate generated in the water-phase washing process into a water-phase washing filtrate storage tank, and replacing the deionized water in the first step ① heating treatment process of the production batch after preparation;
⑤ washing with water at room temperature, and centrifuging
Preparing a filter cake from ④, preparing slurry by using deionized water, feeding the slurry into a room temperature water washing tank, wherein the deionized water accounts for 70-120% of the mass of acetic acid used in the dissolving and decoloring steps in the first step, stirring and washing for 30 minutes in the water washing tank, performing centrifugal filtration, performing solid-liquid separation, drying the filter cake, feeding room temperature water washing filtrate into a room temperature water washing filtrate storage tank, and rinsing ④ aqueous phases in a prepared batch to replace the deionized water for recycling;
⑥ drying
Washing the product with ⑤ items of room temperature water, drying the filter cake after centrifugation by a double-cone vacuum dryer to obtain the mixed long carbon chain dibasic acid product, wherein the product quality reaches the following technical indexes:
6. use of the high purity mixed long carbon chain dicarboxylic acids according to claim 1, characterized by use as surfactants, environmentally friendly high performance semi-synthetic cutting fluids, high grade lubricating oils, synthetic joss-sticks.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321418A (en) * | 2020-11-24 | 2021-02-05 | 淮安清江石油化工有限责任公司 | Refining method of long-chain dibasic acid |
| CN114426476A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Refining method and device for long-chain dibasic acid |
| WO2023001267A1 (en) | 2021-07-23 | 2023-01-26 | 苏州欧丽特生物医药有限公司 | Supramolecular amino acid or salt thereof, and preparation method therefor and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4172086A (en) * | 1977-03-28 | 1979-10-23 | Fmc Corporation | Process for the manufacture of peroxycarboxylic acids |
| CN1552687A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Refining method for long-chain biatomic acid |
| CN1844404A (en) * | 2006-02-14 | 2006-10-11 | 南通圣诺鑫生物科技有限公司 | Process for producing hybrid long chain dicarboxylic acid by microorganism fermentation |
| CN101985416A (en) * | 2010-04-30 | 2011-03-16 | 山东瀚霖生物技术有限公司 | Refining technology for producing long carbon chain dicarboxylic acid by using biological fermentation process |
| CN102010318A (en) * | 2010-04-30 | 2011-04-13 | 山东瀚霖生物技术有限公司 | Method for producing mixed long carbon chain dibasic acid |
| CN109516913A (en) * | 2017-09-18 | 2019-03-26 | 上海凯赛生物技术研发中心有限公司 | Long-chain biatomic acid water phase fusion-crystallization technique |
| CN110002992A (en) * | 2019-03-24 | 2019-07-12 | 张艾琳 | A kind of refining methd of positive long-chain biatomic acid |
-
2019
- 2019-12-31 CN CN201911421671.4A patent/CN111039776A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4172086A (en) * | 1977-03-28 | 1979-10-23 | Fmc Corporation | Process for the manufacture of peroxycarboxylic acids |
| CN1552687A (en) * | 2003-05-31 | 2004-12-08 | 中国石油化工股份有限公司 | Refining method for long-chain biatomic acid |
| CN1844404A (en) * | 2006-02-14 | 2006-10-11 | 南通圣诺鑫生物科技有限公司 | Process for producing hybrid long chain dicarboxylic acid by microorganism fermentation |
| CN101985416A (en) * | 2010-04-30 | 2011-03-16 | 山东瀚霖生物技术有限公司 | Refining technology for producing long carbon chain dicarboxylic acid by using biological fermentation process |
| CN102010318A (en) * | 2010-04-30 | 2011-04-13 | 山东瀚霖生物技术有限公司 | Method for producing mixed long carbon chain dibasic acid |
| CN109516913A (en) * | 2017-09-18 | 2019-03-26 | 上海凯赛生物技术研发中心有限公司 | Long-chain biatomic acid water phase fusion-crystallization technique |
| CN110002992A (en) * | 2019-03-24 | 2019-07-12 | 张艾琳 | A kind of refining methd of positive long-chain biatomic acid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114426476A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Refining method and device for long-chain dibasic acid |
| CN112321418A (en) * | 2020-11-24 | 2021-02-05 | 淮安清江石油化工有限责任公司 | Refining method of long-chain dibasic acid |
| WO2023001267A1 (en) | 2021-07-23 | 2023-01-26 | 苏州欧丽特生物医药有限公司 | Supramolecular amino acid or salt thereof, and preparation method therefor and application thereof |
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Application publication date: 20200421 |