CN105622391A - Purification method for long-chain dicarboxylic acid - Google Patents
Purification method for long-chain dicarboxylic acid Download PDFInfo
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- CN105622391A CN105622391A CN201410585416.4A CN201410585416A CN105622391A CN 105622391 A CN105622391 A CN 105622391A CN 201410585416 A CN201410585416 A CN 201410585416A CN 105622391 A CN105622391 A CN 105622391A
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Abstract
The invention discloses a purification method for long-chain dicarboxylic acid. The purification method includes the steps: I, heating and inactivating a terminated fermentation liquid; II, removing bacterial residues and other solid impurities, and recycling alkanes; III, adding an appropriate amount of polyethylene glycol and glucan to the fermentation liquid, and making the substances dissolved in the fermentation liquid, to prepare an aqueous two-phase system; IV, carrying out hypergravity treatment of the aqueous two-phase system, allowing an upper phase and a lower phase of the mixed system after the hypergravity treatment to be rapidly separated, dissolving proteins and other impurities in the upper phase, and dissolving the product dicarboxylic acid salt in the lower phase; and V, taking the lower phase in the step IV, acidifying to make dicarboxylic acid crystallized and precipitated, cooling, filtering and drying to obtain a refined dicarboxylic acid product. The method adopts the aqueous two-phase extraction and hypergravity to be combined for treating and refining dicarboxylic acid, shortens the technological process, saves the investment of equipment, time and energy consumption and the like, also can obtain the refined product with high purity and low total nitrogen content, and is more suitable for industrialized production.
Description
Technical field
The present invention relates to the method for purification of a kind of long chain dicarboxylic acid, the method particularly obtaining high purity long chain dicarboxylic acids from fermentation liquid.
Background technology
Long chain dicarboxylic acid general molecular formula is CnH2n-2O4, wherein n is 10-18, is that microorganism utilizes the fermentation such as liquid wax and the metabolite that obtains. Its fermentation liquid is complicated heterogeneous system, wherein contain the secretions etc. of unreacted carbon source, microbial cell and fragment, the culture medium not utilized and metabolite and microorganism, especially wherein contain a large amount of protein, pigment and ash to grade impurity, have a strong impact on purity and the application of product, and bring difficulty with refining to the extraction of this kind dicarboxylic acids.
The method extracting long chain dicarboxylic acid at present is generally divided into solvent method and Aqueous phase. Although solvent method can solve the problems referred to above, but owing to solvent method exists investment greatly, equipment corrosion is serious, remains solvent and alkane and the problem such as production security and environmental pollution in product, and the use of the method is greatly limited. Although traditional aqueous phase method of purification overcomes the defect of solvent method, but its product purity and yield can not reach relatively high target.
In long chain dicarboxylic acid process for purification disclosed in CN01142806.6, with long chain dicarboxylic acid dry powder for raw material, use acetone, methanol and ethanol as solvent refining long-chain dicarboxylic acids. Dicarboxylic acids in this method first fermentation liquid is first after activated carbon adsorption, then acidizing crystal, filtration, washing and dry dicarboxylic acid crystallizates filter cake obtain long chain dicarboxylic acid dry powder, then adopts organic solvent to refine. The filter cake that the raw material that the method is refined is moisture obtains dicarboxylic acids dry powder after drying, and raw aqueous quantitative limitation reduces the operating flexibility of the method, adds the equipment that thick acid is dry, causes that this technological process is longer, add production cost. And the method is in the aqueous solution of the alkaline dicarboxylic acids sodium salt obtained before dicarboxylic acid crystallizates filter cake and in solvent refining processes, carry out twice activated carbon adsorption altogether to process, those skilled in the relevant art know about, increase a charcoal treatment process, equipment investment and production cost can be increased, and activated carbon dosage is directly proportional to the loss of product, activated carbon dosage is more big, and the yield of product is more low. And when the refining dicarboxylic acids of organic solvent, adopt adsorbent generally can reach the requirement of decolouring, but still more difficult elimination small molecular protein therein, make total nitrogen content undesirable.
CN1255483A discloses a kind of method of Aqueous phase separation dicarboxylic acids: termination fermentation liquid adds the unreacted alkane of heat extraction, then adds diatom filtration sterilization; Filtrate obtains acid cake and filtrate through adjusting pH value; Filtrate adds again activated carbon decolorizing, then filters; The sour cake obtained before dissolving with the filtrate after decolouring again, acidifying; Finally obtaining crystallization, drying obtains dicarboxylic acid product. The method complex operation step, running cost is high, and dicarboxylic acid product yield is too low, and purity is also not high, and the alkane response rate is low.
Summary of the invention
For the deficiencies in the prior art, the invention provides the method for purification of a kind of long chain dicarboxylic acid. The inventive method adopts aqueous two-phase extraction to be combined the refining dicarboxylic acids of process with hypergravity, not only shorten technological process, save equipment, time and energy consumption etc. to put into, and purity height can be obtained, purified product that total nitrogen content is low, be more suitable for industrialized production.
The method of purification of long chain dicarboxylic acid of the present invention, including herein below:
I, general terminate fermentation liquid heat inactivation;
The solid impurities such as II, removing dreg, reclaim alkane;
III, in fermentation liquid, add appropriate Polyethylene Glycol and glucosan, make each material be dissolved in fermentation liquid, make double-aqueous phase system;
IV, above-mentioned double-aqueous phase system being carried out hypergravity process, the impurity such as mixed system is biphase up and down after hypergravity processes to be rapidly separated, albumen are dissolved in phase, and product dicarboxylate is dissolved in lower phase;
V, taking in step IV lower phase, acidifying makes dicarboxylic acid crystallizates precipitate out, cooling, filters, dries the dicarboxylic acid product obtaining refining.
In the inventive method, terminating fermentation liquid described in step I is the metabolite that microorganism utilizes that the fermentation of liquid wax obtains, and the dicarboxylic acid molecule formula wherein contained is CnH2n-2O4, wherein n is 10-18, and dicarboxylic acids can be single a kind of dicarboxylic acids, it is also possible to be mixed dicarboxylic acid. Described fermentation liquid heat inactivation temperature is generally 75 DEG C��100 DEG C.
In the inventive method, step II can adopt the conventional methods such as centrifugal or membrane filtration and equipment to carry out the operation of the impurity such as elimination thalline.
In the inventive method, the molecular weight of the Polyethylene Glycol described in step III is 4000��40000, it is preferred to 4000��20000, and mass fraction is 2%��8%, it is preferred to 3%��6%; The molecular weight of glucosan is 100000��500000, it is preferred to 300000��500000, and mass fraction is 3%��10%, it is preferred to 5%��8%. The partition coefficient utilizing the impurity such as albumen, foreign protein pigment, nucleic acid biphase in aqueous two-phase from product is different thus carrying out product extraction. In the present invention, it is also possible to being simultaneously introduced a certain amount of phosphate, concentration is at 0.005��0.02mol/L. Phosphate can be sodium ascorbyl phosphate or potassium phosphate, it is preferable that disodium hydrogen phosphate or dipotassium hydrogen phosphate. The phosphate wherein added on the one hand can as the pH of buffer agent regulation system, on the one hand owing to the different valence state acid group of phosphoric acid is different at the partition coefficient of double-aqueous phase system, thus interphase potential difference can be regulated by adding different phosphate ratio and concentration, thus affecting the distribution of material.
In the inventive method, the hypergravity level that step IV hypergravity processes is 10��650g(g is acceleration of gravity=9.8m/s2), the mean residence time that hypergravity processes is 0.2��10s, and hypergravity equipment is high gravity rotating packed bed, the conventional hypergravity rotary apparatus such as deflector type, screw path type, rotating compact disc formula and fixed-rotator type, it is preferable that high gravity rotating packed bed. Hypergravity level refers to that supergravity reactor rotor rotates the size of the centrifugal acceleration produced, and the multiple typically by gravity acceleration g represents, main relevant with the internal-and external diameter of the rotating speed of rotor and rotor.
In the inventive method, in step V, acidifying can adopt conventional method to carry out. The pH value of described acidifying is 2.0��4.0, and heating-up temperature is 80��100 DEG C. The acid used by acidifying that the present invention is above-mentioned can be the H of any concentration2SO4��HNO3, HCl or H3PO4��
In the inventive method, till in step V, crystallisation by cooling temperature is generally and makes dicarboxylic acids sufficient crystallising, temperature is generally 10��30 DEG C. Filtration step in step V can adopt membrane filtration, and such as NF membrane or micro-filtration membrane etc., available membrane aperture ranges for 10-3��m��10 ��m.
The inventive method can obtain the dicarboxylic acid product of highly purified single kind, it is also possible to obtain mixed dicarboxylic acid product.
Compared with prior art, the invention have the advantages that
(1) aqueous two-phase extraction is adopted to purify long chain dicarboxylic acid, the different product that realizes of the partition coefficient that utilizes impurity to be separated biphase in aqueous two-phase from product dicarboxylic acids extracts, avoid extract by solvents and introduce the problems such as the production security that brings of organic solvent and environmental pollution, solve the problem that the product purity that Aqueous phase extracts is difficult to reach high requirement simultaneously.
(2) adopt aqueous two-phase extraction to process the method combined with hypergravity and extract long chain dicarboxylic acid, hypergravity process is utilized significantly to enhance interphase mass transfer, it is effectively improved effect of extracting so that the impurity such as albumen, foreign protein pigment, nucleic acid and product better alternate separate two; Hypergravity processes and the time extracted with point phase is greatly shortened simultaneously, and the time that saves puts into.
(3) process route adopted is prone to industry amplification, and operating condition is gentle, can save energy consumption and material consumption.
Detailed description of the invention
Come by the examples below further the inventive method to be explained.
Embodiment 1
With n-dodecane hydrocarbon for substrate, utilize candida tropicalis fermenting and producing 12 carbon dicarboxylic acids. During fermentation ends, dicarboxylic acids concentration is 164.3g/L, pH is 7.4. Taking fermentation liquid 1000ml, heating, to 80 DEG C, stands 2h, reclaims the unreacted alkane in upper strata, is 10 by membrane aperture-2��m membrane filtration, remove somatic cells, fragment. Adding Polyethylene Glycol that mass fraction 5%, molecular weight are 4000 in fermentation liquid and mass fraction 8%, molecular weight are the glucosan of 300000, stirring makes each material be dissolved in fermentation liquid, forms double-aqueous phase system. System being sent into and carry out hypergravity process in hypergravity equipment, hypergravity level is 150g, and the mean residence time that hypergravity processes is 5s, the static 20min of system that will process through hypergravity, by upper and lower two-phase laminated flow, takes off phase, with the sulfur acid for adjusting pH of 6M to 3 and heat to 85 DEG C, constant temperature 1h. At the uniform velocity it is down to crystallizing at room temperature with 15 DEG C/h, is 10 by membrane aperture-2��m ultrafiltration membrance filter obtain dicarboxylic acids filter cake, be washed to neutrality, namely dry cake obtains product. Product quality is in Table 1.
Embodiment 2
With n-dodecane hydrocarbon for substrate, utilize candida tropicalis fermenting and producing 12 carbon dicarboxylic acids. During fermentation ends, dicarboxylic acids concentration is 158g/L, pH is 7.3. Taking fermentation liquid 1000ml, heating, to 95 DEG C, stands 2h, reclaims the unreacted alkane in upper strata, is 10 by membrane aperture-1��m micro-filtrate membrane filtration, remove somatic cells, fragment. In fermentation liquid add mass fraction 3% molecular weight be 20000 Polyethylene Glycol and mass fraction 5% molecular weight be the glucosan of 500000, stirring make each material be dissolved in fermentation liquid, formed double-aqueous phase system. System being sent into and carry out hypergravity process in hypergravity equipment, hypergravity level is 200g, and the mean residence time that hypergravity processes is 8s, the static 30min of system that will process through hypergravity, by upper and lower two-phase laminated flow, takes off phase, with the sulfur acid for adjusting pH of 5M to 2 and heat to 90 DEG C, constant temperature 1h. At the uniform velocity it is down to crystallizing at room temperature with 20 DEG C/h, is 10 by membrane aperture-2��m ultrafiltration membrance filter obtain dicarboxylic acids filter cake, be washed to neutrality, namely dry cake obtains product. Product quality is in Table 1.
Embodiment 3
With n-tridecane hydrocarbon for substrate, utilize candida tropicalis fermenting and producing 13 carbon dicarboxylic acids. During fermentation ends, dicarboxylic acids concentration is 154.3g/L, pH is 7.5. Taking fermentation liquid 1000ml, heating, to 80 DEG C, stands 2h, reclaims the unreacted alkane in upper strata, is 10 by membrane aperture-2��m ultrafiltration membrance filter, remove somatic cells, fragment. In fermentation liquid add mass fraction 4% molecular weight be 10000 Polyethylene Glycol and mass fraction 6% molecular weight be the glucosan of 400000, stirring make each material be dissolved in fermentation liquid, formed double-aqueous phase system. System being sent into and carry out hypergravity process in hypergravity equipment, hypergravity level is 300g, and the mean residence time that hypergravity processes is 3s, the static 30min of system that will process through hypergravity, by upper and lower two-phase laminated flow, takes off phase, with the sulfur acid for adjusting pH of 8M to 2.5 and heat to 95 DEG C, constant temperature 1h. At the uniform velocity it is down to crystallizing at room temperature with 18 DEG C/h, is 10 by membrane aperture-2��m ultrafiltration membrance filter obtain dicarboxylic acids filter cake, be washed to neutrality, namely dry cake obtains product. Product quality is in Table 1.
Embodiment 4
With n-tridecane hydrocarbon for substrate, utilize candida tropicalis fermenting and producing 13 carbon dicarboxylic acids. During fermentation ends, dicarboxylic acids concentration is 158.8g/L, pH is 7.2. Taking fermentation liquid 1000ml, heating, to 95 DEG C, stands 1.5h, reclaims the unreacted alkane in upper strata, is 10 by membrane aperture-2��m ultrafiltration membrance filter, remove somatic cells, fragment. In fermentation liquid add mass fraction 6% molecular weight be 6000 Polyethylene Glycol and mass fraction 7% molecular weight be the glucosan of 300000, stirring make each material be dissolved in fermentation liquid, formed double-aqueous phase system. System being sent into and carry out hypergravity process in hypergravity equipment, hypergravity level is 350g, and the mean residence time that hypergravity processes is 4s, the static 30min of system that will process through hypergravity, by upper and lower two-phase laminated flow, takes off phase, with the sulfur acid for adjusting pH of 5M to 3.5 and heat to 90 DEG C, constant temperature 1h. At the uniform velocity it is down to crystallizing at room temperature with 16 DEG C/h, is 10 by membrane aperture-2��m ultrafiltration membrance filter obtain dicarboxylic acids filter cake, be washed to neutrality, namely dry cake obtains product. Product quality is in Table 1.
Embodiment 5
With n-dodecane hydrocarbon for substrate, utilize candida tropicalis fermenting and producing 12 carbon dicarboxylic acids. During fermentation ends, dicarboxylic acids concentration is 155.6g/L, pH is 7.6. Taking fermentation liquid 1000ml, heating, to 92 DEG C, stands 1.5h, reclaims the unreacted alkane in upper strata, is 10 by membrane aperture-2��m ultrafiltration membrance filter, remove somatic cells, fragment. In fermentation liquid add mass fraction 6% molecular weight be 10000 Polyethylene Glycol and mass fraction 8% molecular weight be the glucosan of 300000, stirring make each material be dissolved in fermentation liquid, formed double-aqueous phase system. System being sent into and carry out hypergravity process in hypergravity equipment, hypergravity level is 400g, and the mean residence time that hypergravity processes is 2s, the static 20min of system that will process through hypergravity, by upper and lower two-phase laminated flow, takes off phase, with the sulfur acid for adjusting pH of 7M to 4.0 and heat to 95 DEG C, constant temperature 1h. At the uniform velocity it is down to crystallizing at room temperature with 20 DEG C/h, is 10 by membrane aperture-2��m ultrafiltration membrance filter obtain dicarboxylic acids filter cake, be washed to neutrality, namely dry cake obtains product. Product quality is in Table 1.
Embodiment 6
Adding the dipotassium hydrogen phosphate of molar concentration 0.005mol/L in fermentation liquid, all the other conditions are with embodiment 1. Product quality is in Table 1.
Embodiment 7
Adding the disodium hydrogen phosphate of molar concentration 0.02mol/L in fermentation liquid, all the other conditions are with embodiment 2. Product quality is in Table 1.
Embodiment 8
Adding the dipotassium hydrogen phosphate of molar concentration 0.01mol/L in fermentation liquid, all the other conditions are with embodiment 3. Product quality is in Table 1.
Comparative example 1
Double-aqueous phase system does not carry out hypergravity process, and uses common centrifugal treating, and centrifugation time 5min, centrifugal rotational speed 5000rpm, all the other are with embodiment 1, and product quality is in Table 1.
Table 1 long chain dicarboxylic acid product quality
As shown in Table 1, long chain dicarboxylic acid product purity prepared by the inventive method is high, and total nitrogen content is low, is more suitable for industrialized production.
Claims (11)
1. the method for purification of a long chain dicarboxylic acid, it is characterised in that include herein below:
I, general terminate fermentation liquid heat inactivation;
The solid impurities such as II, removing dreg, reclaim alkane;
III, in fermentation liquid, add appropriate Polyethylene Glycol and glucosan, make each material be dissolved in fermentation liquid, make double-aqueous phase system;
IV, above-mentioned double-aqueous phase system being carried out hypergravity process, the impurity such as mixed system is biphase up and down after hypergravity processes to be rapidly separated, albumen are dissolved in phase, and product dicarboxylate is dissolved in lower phase;
V, taking in step IV lower phase, acidifying makes dicarboxylic acid crystallizates precipitate out, cooling, filters, dries the dicarboxylic acid product obtaining refining.
2. in accordance with the method for claim 1, it is characterised in that: terminating fermentation liquid described in step I is the metabolite that microorganism utilizes that the fermentation of liquid wax obtains, and the dicarboxylic acid molecule formula wherein contained is CnH2n-2O4, wherein n is 10-18, and dicarboxylic acids can be single a kind of dicarboxylic acids, it is also possible to be mixed dicarboxylic acid.
3. in accordance with the method for claim 1, it is characterised in that: the fermentation liquid heat inactivation temperature described in step I is 75 DEG C��100 DEG C.
4. in accordance with the method for claim 1, it is characterised in that: the molecular weight of the Polyethylene Glycol described in step III is 4000��40000, and mass fraction is 2%��8%; The molecular weight of glucosan is 100000��500000, and mass fraction is 3%��10%.
5. in accordance with the method for claim 4, it is characterised in that: the molecular weight of the Polyethylene Glycol described in step III is 4000��20000, and mass fraction is 3%��6%; The molecular weight of glucosan is 300000��500000, and mass fraction is 5%��8%.
6. in accordance with the method for claim 1, it is characterised in that: being simultaneously introduced a certain amount of phosphate in the double-aqueous phase system described in step III, concentration is 0.005��0.02mol/L.
7. in accordance with the method for claim 6, it is characterised in that: phosphate is sodium ascorbyl phosphate or potassium phosphate.
8. in accordance with the method for claim 1, it is characterised in that: the hypergravity level that step IV hypergravity processes is 10��650g(g is acceleration of gravity=9.8m/s2), the mean residence time that hypergravity processes is 0.2��10s, and hypergravity equipment is high gravity rotating packed bed, deflector type, screw path type, rotating compact disc formula or fixed-rotator type hypergravity rotary apparatus, it is preferable that high gravity rotating packed bed.
9. in accordance with the method for claim 1, it is characterised in that: the pH value of acidifying described in step V is 2.0��4.0, and heating-up temperature is 80��100 DEG C; Acid used by acidifying is the H of any concentration2SO4��HNO3, HCl or H3PO4��
10. in accordance with the method for claim 1, it is characterised in that: in step V, crystallisation by cooling temperature is 10��30 DEG C.
11. in accordance with the method for claim 1, it is characterised in that: the filtration in step V adopts NF membrane or micro-filtration membrane, and membrane aperture ranges for 10-3��m��10 ��m.
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| CN114685260A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Method for purifying long-chain dicarboxylic acid |
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| CN102796775A (en) * | 2011-05-26 | 2012-11-28 | 中国科学院城市环境研究所 | Method for extracting lactic acid fermentation product of kitchen waste |
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| CN114685260A (en) * | 2020-12-29 | 2022-07-01 | 中国石油化工股份有限公司 | Method for purifying long-chain dicarboxylic acid |
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Effective date of registration: 20230818 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |