CN114890872B - Method for improving stability of 2, 5-di-tert-butylhydroquinone - Google Patents
Method for improving stability of 2, 5-di-tert-butylhydroquinone Download PDFInfo
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- CN114890872B CN114890872B CN202210743287.1A CN202210743287A CN114890872B CN 114890872 B CN114890872 B CN 114890872B CN 202210743287 A CN202210743287 A CN 202210743287A CN 114890872 B CN114890872 B CN 114890872B
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- butylhydroquinone
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- 238000000034 method Methods 0.000 title claims abstract description 41
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 title claims description 17
- 238000001035 drying Methods 0.000 claims abstract description 78
- 239000012043 crude product Substances 0.000 claims abstract description 68
- 239000000047 product Substances 0.000 claims abstract description 56
- JFGVTUJBHHZRAB-UHFFFAOYSA-N 2,6-Di-tert-butyl-1,4-benzenediol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1O JFGVTUJBHHZRAB-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000000843 powder Substances 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002425 crystallisation Methods 0.000 claims abstract description 28
- 230000008025 crystallization Effects 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 20
- 238000005119 centrifugation Methods 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000012071 phase Substances 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- 239000007790 solid phase Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 5
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 229940001584 sodium metabisulfite Drugs 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 239000004250 tert-Butylhydroquinone Substances 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 3
- 239000012141 concentrate Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 50
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 16
- 238000001816 cooling Methods 0.000 description 12
- 238000007789 sealing Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 3
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/86—Purification; separation; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/82—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/70—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment
- C07C37/84—Purification; separation; Use of additives, e.g. for stabilisation by physical treatment by crystallisation
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for improving the stability of 2, 5-ditert-butylhydroquinone, and relates to the technical field of 2, 5-ditert-butylhydroquinone purification. The method of the invention comprises the following steps: dissolving the D-TBHQ crude product in alcohol added with active metal, heating to 70-75 ℃, dropwise adding dilute acid, and obtaining a crude product solution after the dropwise adding is completed, wherein the mass ratio of the D-TBHQ crude product to the active metal to the dilute acid is 1: (0.005-0.007): (0.01-0.015); the crude product solution is subjected to decoloring, concentration, crystallization, centrifugation, drying and crushing in sequence to obtain a D-TBHQ product; wherein, concentrate: adding a reducing agent into the decolored crude product decolored solution according to the mass percentage, and concentrating to obtain concentrated solution; and (3) drying: and putting the powder obtained by centrifugation into a drying oven for drying, and exhausting the drying oven for 0.5-1 h before the drying process. The D-TBHQ prepared by the method has high stability and a shelf life of 1 year, and solves the problems of poor stability and short shelf life of the existing D-TBHQ.
Description
Technical Field
The invention relates to the technical field of 2, 5-ditert-butylhydroquinone purification, in particular to a method for improving the stability of 2, 5-ditert-butylhydroquinone.
Background
2, 5-Di-tert-butyl hydroquinone, called D-TBHQ for short, is a nontoxic, non-bad smell and pollution-free plastic inhibitor, is used as an antioxidant for natural rubber, synthetic rubber and latex, and can ensure that unsaturated polyester has good stability in the production and storage processes, and is widely used in the industries of synthetic rubber, plastic, resin and the like.
The industrial production of 2, 5-ditert-butylhydroquinone generally takes tertiary butanol and hydroquinone as raw materials, takes p-toluenesulfonic acid aqueous solution as a catalyst to react, obtains a 2, 5-ditert-butylhydroquinone crude product by the method, obtains a 2, 5-ditert-butylhydroquinone product after purifying the 2, 5-ditert-butylhydroquinone crude product, and has poor stability and long-term storage difficulty because the 2, 5-ditert-butylhydroquinone product prepared by the existing purification method usually has a storage time of about 7 days, and therefore, the product needs to be immediately used after preparation.
Disclosure of Invention
Aiming at the problems of the background technology, the invention aims to provide a method for improving the stability of 2, 5-ditert-butylhydroquinone, the prepared 2, 5-ditert-butylhydroquinone has high stability and a shelf life of 1 year, and the problems of poor stability and short shelf life of the existing 2, 5-ditert-butylhydroquinone are solved.
To achieve the purpose, the invention adopts the following technical scheme:
A method for improving the stability of 2, 5-ditertbutyl hydroquinone, comprising the following steps:
(1) Dissolving a2, 5-ditert-butylhydroquinone crude product in alcohol added with active metal, heating to 70-75 ℃, dropwise adding dilute acid, and obtaining a crude product solution after the dropwise adding, wherein the mass ratio of the 2, 5-ditert-butylhydroquinone crude product to the active metal to the dilute acid is 1: (0.005-0.007): (0.01-0.015);
(2) The crude product solution is subjected to decoloring, concentration, crystallization, centrifugation, drying and crushing in sequence to obtain a 2, 5-ditert-butylhydroquinone product;
The operation method of concentration is as follows: adding 0.5-3% of reducing agent into the decolored crude product decolored solution according to the mass percentage, and concentrating to obtain concentrated solution;
The operation method of drying is as follows: and putting the powder obtained by centrifugation into a drying oven for drying for 8-12 hours, and exhausting the drying oven for 0.5-1 hour before the drying process.
Further, in the step (1), the mass ratio of the active metal to the dilute acid is 1:2 to 3.
Further, in the step (1), the active metal is zinc or aluminum.
Further, in the step (1), the dilute acid is dilute hydrochloric acid or dilute sulfuric acid.
Further, in the step (2), the reducing agent is any one of sodium sulfite, sodium dithionite and sodium metabisulfite.
Further, in the step (2), the decoloring operation method is as follows: adding active carbon into the crude product solution at 60-65 ℃ for decoloring for 0.5h, and filtering to obtain the crude product decolored solution.
Further, in the step (2), the crystallization operation method is as follows: after the temperature of the concentrated solution is reduced to 25-35 ℃, crystals are precipitated.
Further, in the step (2), the centrifugation operation method is as follows: and (3) placing the precipitated phase after crystallization in a centrifugal machine, adding 3 times of alcohol, performing centrifugal washing and throwing, discarding the liquid phase after the centrifugal throwing is finished, and taking out the solid phase to form powder.
The 2, 5-ditert-butylhydroquinone is prepared by the method for improving the stability of the 2, 5-ditert-butylhydroquinone.
The technical scheme has the following beneficial effects: according to the technical scheme, when the method is used for concentrating, 0.5% -3% of reducing agent is added, so that the stability of the 2, 5-di-tert-butyl hydroquinone (D-TBHQ) can be effectively improved, the antioxidation period of the D-TBHQ is increased, and the quality of a product is improved.
Detailed Description
The technical scheme of the invention is further described below with reference to the specific embodiments.
A method for improving the stability of 2, 5-ditertbutyl hydroquinone, comprising the following steps:
(1) Dissolving a2, 5-ditert-butylhydroquinone crude product in alcohol added with active metal, heating to 70-75 ℃, dropwise adding dilute acid, and obtaining a crude product solution after the dropwise adding, wherein the mass ratio of the 2, 5-ditert-butylhydroquinone crude product to the active metal to the dilute acid is 1: (0.005-0.007): (0.01-0.015);
(2) The crude product solution is subjected to decoloring, concentration, crystallization, centrifugation, drying and crushing in sequence to obtain a 2, 5-ditert-butylhydroquinone product;
The operation method of concentration is as follows: adding 0.5-3% of reducing agent into the decolored crude product decolored solution according to the mass percentage, and concentrating to obtain concentrated solution;
The operation method of drying is as follows: and putting the powder obtained by centrifugation into a drying oven for drying for 8-12 hours, and exhausting the drying oven for 0.5-1 hour before the drying process.
It is worth to say that, when the method of the technical scheme is used for concentrating, 0.5% -3% of reducing agent is added, so that the stability of the 2, 5-di-tert-butyl hydroquinone (D-TBHQ) can be effectively improved, the antioxidation period of the D-TBHQ is increased, and the quality of the product is improved, meanwhile, as the 2, 5-di-tert-butyl hydroquinone is prepared from tert-butyl alcohol and hydroquinone as raw materials, a small amount of hydroquinone can remain in the 2, 5-di-tert-butyl hydroquinone crude product, if Hydroquinone (HQ) exists in the 2, 5-di-tert-butyl hydroquinone product, the stability of the product is poor, the product can be reddish and ash after being placed for only a few days, and the scrapped treatment is caused, therefore, the technical scheme is used for carrying out the air draft treatment on the oven in the first 0.5-1 h of the drying process, and because the Hydroquinone (HQ) can be evaporated in the drying process of the oven, the impurities hydroquinone can be removed by taking away by the air draft fan, and the whiteness and the stability of the 2, 5-di-tert-butyl hydroquinone can be effectively improved, and the red-butyl hydroquinone produced can not reach the quality of the red-grey after a year.
Further illustratively, in step (1), the ratio by mass of crude 2, 5-di-tert-butylhydroquinone, said active metal and said dilute acid is controlled to be 1: (0.005-0.007): (0.01-0.015), the active metal and the dilute acid can react to generate hydrogen, the hydrogen can reduce quinone impurities in the D-TBHQ crude product into 2, 5-ditert-butylhydroquinone, and the yield of the product can be improved.
Specifically, in the concentration process, 0.5% -3% of reducing agent is added, so that the oxidation resistance period of 2, 5-di-tert-butylhydroquinone (D-TBHQ) can be effectively improved, if the addition amount of the reducing agent is too low, the oxidation resistance period is shorter, and if the addition amount of the reducing agent is too high, raw materials are wasted, and the production cost is increased.
Therefore, by adopting the method of the technical scheme, the high-quality 2, 5-ditert-butylhydroquinone product can be obtained, meanwhile, the production cost can be saved, and obvious economic benefit can be obtained after the large-scale production is carried out.
Further illustratively, in step (1), the mass ratio of the active metal to the dilute acid is 1:2 to 3;
The concentration of the dilute acid is 32%.
It is noted that, in step (1), by setting the mass ratio of the active metal to the dilute acid to 1: 2-3, the active metal and the dilute acid can react more to generate hydrogen, and the hydrogen can reduce quinone impurities in the D-TBHQ crude product into 2, 5-ditert-butylhydroquinone, thereby further improving the yield of the product.
Further illustratively, in step (1), the active metal is zinc or aluminum.
Further illustratively, in step (1), the dilute acid is dilute hydrochloric acid or dilute sulfuric acid.
According to the technical scheme, active metal zinc or aluminum is selected, and the zinc or aluminum can be easily reacted with dilute acid (dilute hydrochloric acid or dilute sulfuric acid) to generate hydrogen, so that quinone impurities in a D-TBHQ crude product can be reduced into the D-TBHQ, and the yield of products is improved.
Further, in the step (2), the reducing agent is any one of sodium sulfite, sodium dithionite and sodium metabisulfite.
Further illustratively, in the step (2), the decoloring is performed as follows: adding active carbon into the crude product solution at 60-65 ℃ for decoloring for 0.5h, and filtering to obtain the crude product decolored solution.
The whiteness of the 2, 5-ditert-butylhydroquinone product can be effectively improved by adding activated carbon for decoloring, so that the quality of the product is improved.
Further, in the step (2), the crystallization operation method is as follows: after the temperature of the concentrated solution is reduced to 25-35 ℃, crystals are precipitated.
The temperature is reduced to 25-35 ℃,2, 5-ditert-butylhydroquinone can be crystallized, if the temperature is too high, most of 2, 5-ditert-butylhydroquinone still dissolves in alcohol at the moment and cannot be separated out, if the temperature is too low, the requirement on production equipment is too high, and the production cost can be increased.
Further illustratively, in step (2), the centrifugation is performed as follows: and (3) placing the precipitated phase after crystallization in a centrifugal machine, adding 3 times of alcohol, performing centrifugal washing and throwing, discarding the liquid phase after the centrifugal throwing is finished, and taking out the solid phase to form powder.
It is worth to say that, during centrifugation, 3 times of volume of alcohol is added for centrifugal washing and throwing, the whiteness and stability of the 2, 5-di-tert-butylhydroquinone product can be effectively improved, so that the shelf life is longer, and if the material is not washed by alcohol during centrifugation, the prepared 2, 5-di-tert-butylhydroquinone product is easy to reddish, the stability is poor, and the shelf life is short.
The 2, 5-ditert-butylhydroquinone is prepared by the method for improving the stability of the 2, 5-ditert-butylhydroquinone.
The present technology will be further described with reference to examples.
Example 1
The implementation method for improving the stability of the 2, 5-ditert-butylhydroquinone comprises the following steps:
100g of 2, 5-ditert-butylhydroquinone crude product is added into 95% alcohol with the volume of 2 times, 0.5g of active metal (zinc) is added, after the temperature is raised to 70 ℃ for dissolution, 1g of 32% diluted hydrochloric acid is added dropwise, the adding time is 0.5h, and a crude product solution is obtained after the adding is completed;
(2) The crude product solution is subjected to decoloring, concentration, crystallization, centrifugation, drying and crushing in sequence to obtain a 2, 5-ditert-butylhydroquinone product;
Decoloring: adding active carbon into the crude product solution, stirring at 60 ℃ for decoloring for 0.5h, and filtering to obtain a crude product decoloring solution;
concentrating: adding 1g of reducing agent (sodium bisulphite) into the decolored crude product decolored solution according to the mass percentage, mixing and stirring, concentrating for 4 hours, and stopping concentrating after 75% of alcohol is concentrated to obtain concentrated solution;
Crystallization: cooling and crystallizing after the temperature of the material is reduced to 35 ℃;
And (3) centrifuging: placing the precipitated phase after crystallization in a centrifuge, adding 3 times of alcohol, performing centrifugal washing and throwing, discarding the liquid phase after the centrifugal throwing is finished, taking out the solid phase to form powder, placing the powder in a drying chamber to wait for drying, and placing the powder in the drying chamber to wait for drying for less than 24 hours;
and (3) drying: putting the centrifuged powder into a drying oven for drying for 12 hours, and exhausting the drying oven in the first 1 hour of the drying process;
crushing: and naturally cooling the dried powder, crushing the powder by a crusher within 8 hours, and sealing and packaging to obtain a2, 5-ditert-butylhydroquinone product.
Specifically, the content of D-TBHQ in the prepared 2, 5-ditert-butylhydroquinone product reaches 99.689 percent through gas phase detection, meanwhile, the whiteness of the product is detected to be more than 90 degrees, the D-TBHQ prepared in the embodiment 1 does not turn red or become grey within 1 year, and the whiteness is still more than 90 degrees, so that the D-TBHQ product prepared in the embodiment has good quality and good stability, the shelf life reaches 1 year under the normal temperature PE sealing condition, insoluble substances are qualified, and the product yield is improved by 10.5 percent compared with the original technology.
Example 2
The implementation method for improving the stability of the 2, 5-ditert-butylhydroquinone comprises the following steps:
200g of 2, 5-ditert-butylhydroquinone crude product is added into 95% alcohol with the volume of 2 times, 1.2g of active metal (aluminum) is added, after the temperature is raised to 75 ℃ for dissolution, 3g of dilute hydrochloric acid with the concentration of 32% is added dropwise, the adding time is 0.5h, and a crude product solution is obtained after the adding is completed;
(2) The crude product solution is subjected to decoloring, concentration, crystallization, centrifugation, drying and crushing in sequence to obtain a 2, 5-ditert-butylhydroquinone product;
Decoloring: adding active carbon into the crude product solution, stirring at 65 ℃ for decoloring for 0.5h, and filtering to obtain a crude product decoloring solution;
Concentrating: adding 1g of reducing agent (sodium metabisulfite) into the decolored crude product decolored solution according to the mass percentage, mixing and stirring, concentrating for 4 hours, and stopping concentrating after 75% of alcohol is concentrated to obtain concentrated solution;
crystallization: cooling and crystallizing after the temperature of the material is reduced to 25-35 ℃;
And (3) centrifuging: placing the precipitated phase after crystallization in a centrifuge, adding 3 times of alcohol, performing centrifugal washing and throwing, discarding the liquid phase after centrifugal throwing, and taking out the solid phase to form powder;
and (3) drying: putting the centrifuged powder into a drying oven for drying for 8 hours, and exhausting the drying oven for the first 1 hour of the drying process;
crushing: and naturally cooling the dried powder, crushing the powder by a crusher within 8 hours, and sealing and packaging to obtain a2, 5-ditert-butylhydroquinone product.
Specifically, through gas phase detection, the content of D-TBHQ in the prepared 2, 5-ditert-butylhydroquinone product reaches 99.735%, meanwhile, the whiteness of the product is detected to be more than 90 ℃, the D-TBHQ prepared by the embodiment does not turn red or grey within 1 year, and the whiteness is still more than 90 degrees, so that the D-TBHQ product prepared by the embodiment has high stability, the shelf life reaches 1 year under the normal temperature PE sealing condition, the quality is good, the product yield is improved by 12.5% compared with the original technology, and insoluble matters are qualified.
Example 3
The implementation method for improving the stability of the 2, 5-ditert-butylhydroquinone comprises the following steps:
150g of 2, 5-ditert-butylhydroquinone crude product is added into 95% alcohol with the volume of 2 times, 0.75g of active metal (aluminum) is added, after the temperature is raised to 73 ℃ for dissolution, 1.5g of dilute sulfuric acid with the concentration of 32% is added dropwise, the adding time is 0.5h, and a crude product solution is obtained after the adding is completed;
(2) The crude product solution is subjected to decoloring, concentration, crystallization, centrifugation, drying and crushing in sequence to obtain a 2, 5-ditert-butylhydroquinone product;
decoloring: adding active carbon into the crude product solution, stirring at 62 ℃, decoloring for 0.5h, and filtering to obtain a crude product decolored solution;
Concentrating: adding 2g of reducing agent (sodium bisulphite) into the decolored crude product decolored solution according to the mass percentage, mixing and stirring, concentrating for 4 hours, and stopping concentrating after 75% of alcohol is concentrated to obtain concentrated solution;
crystallization: cooling and crystallizing after the temperature of the material is reduced to 25-35 ℃;
And (3) centrifuging: placing the precipitated phase after crystallization in a centrifuge, adding 3 times of alcohol, performing centrifugal washing and throwing, discarding the liquid phase after centrifugal throwing, and taking out the solid phase to form powder;
And (3) drying: putting the centrifuged powder into a drying oven for drying for 8 hours, and exhausting the drying oven for 0.5 hour before the drying process;
crushing: and naturally cooling the dried powder, crushing the powder by a crusher within 8 hours, and sealing and packaging to obtain a2, 5-ditert-butylhydroquinone product.
Specifically, the content of D-TBHQ in the prepared 2, 5-ditert-butylhydroquinone product reaches 99.675 percent through gas phase detection, meanwhile, the whiteness of the product is detected to be more than 90 degrees, the D-TBHQ prepared by the embodiment does not turn red or become grey within 1 year, the whiteness is still more than 90 degrees, the product yield is improved by 9.5 percent compared with the original technology, and insoluble substances are qualified, so that the D-TBHQ product prepared by the embodiment has high stability and good quality, and the shelf life reaches 1 year under the normal-temperature PE sealing condition.
Example 4
The implementation method for improving the stability of the 2, 5-ditert-butylhydroquinone comprises the following steps:
150g of 2, 5-ditert-butylhydroquinone crude product is added into 95% alcohol with the volume of 2 times, 0.75g of active metal (zinc) is added, after the temperature is raised to 70 ℃ for dissolution, 1.5g of dilute sulfuric acid with the concentration of 32% is added dropwise, the adding time is 0.5h, and a crude product solution is obtained after the adding is completed;
(2) The crude product solution is subjected to decoloring, concentration, crystallization, centrifugation, drying and crushing in sequence to obtain a 2, 5-ditert-butylhydroquinone product;
Decoloring: adding active carbon into the crude product solution, stirring at 60 ℃ for decoloring for 0.5h, and filtering to obtain a crude product decoloring solution;
Concentrating: adding 2g of reducing agent (sodium hydrosulfite) into the decolored crude product decolored solution according to the mass percentage, mixing and stirring, concentrating for 4 hours, and stopping concentrating after 75% alcohol is concentrated to obtain concentrated solution;
Crystallization: cooling and crystallizing after the temperature of the material is reduced to 35 ℃;
And (3) centrifuging: placing the precipitated phase after crystallization in a centrifuge, adding 3 times of alcohol, performing centrifugal washing and throwing, discarding the liquid phase after the centrifugal throwing is finished, taking out the solid phase to form powder, placing the powder in a drying chamber to wait for drying, and placing the powder in the drying chamber to wait for drying for less than 24 hours;
And (3) drying: putting the centrifuged powder into a drying oven for drying for 8 hours, and exhausting the drying oven for 0-0.5 hour in the drying process;
crushing: and naturally cooling the dried powder, crushing the powder by a crusher within 8 hours, and sealing and packaging to obtain a2, 5-ditert-butylhydroquinone product.
Specifically, the content of D-TBHQ in the prepared 2, 5-ditert-butylhydroquinone product reaches 99.695 percent through gas phase detection, meanwhile, the whiteness of the product is detected to be more than 90 degrees, the D-TBHQ prepared by the embodiment does not turn red or become grey within 1 year, the whiteness is still more than 90 degrees, the product yield is improved by 9.5 percent compared with the original technology, and insoluble substances are qualified, so that the D-TBHQ product prepared by the embodiment has high stability and good quality, and the shelf life reaches 1 year under the normal-temperature PE sealing condition.
Example 5
The implementation method for improving the stability of the 2, 5-ditert-butylhydroquinone comprises the following steps:
200g of 2, 5-ditert-butylhydroquinone crude product is added into 95% alcohol with the volume of 2 times, 1g of active metal (zinc) is added, after the temperature is raised to 75 ℃ for dissolution, 2g of dilute sulfuric acid with the concentration of 32% is added dropwise, the adding time is 0.5h, and a crude product solution is obtained after the adding is completed;
(2) The crude product solution is subjected to decoloring, concentration, crystallization, centrifugation, drying and crushing in sequence to obtain a 2, 5-ditert-butylhydroquinone product;
decoloring: adding active carbon into the crude product solution, stirring at 64 ℃ for decoloring for 0.5h, and filtering to obtain a crude product decoloring solution;
Concentrating: adding 5g of reducing agent (sodium bisulphite) into the decolored crude product decolored solution according to the mass percentage, mixing and stirring, concentrating for 4 hours, and stopping concentrating after 75% of alcohol is concentrated to obtain concentrated solution;
crystallization: cooling and crystallizing after the temperature of the material is reduced to 30 ℃;
And (3) centrifuging: placing the precipitated phase after crystallization in a centrifuge, adding 3 times of alcohol, performing centrifugal washing and throwing, discarding the liquid phase after the centrifugal throwing is finished, taking out the solid phase to form powder, placing the powder in a drying chamber to wait for drying, and placing the powder in the drying chamber to wait for drying for less than 24 hours;
And (3) drying: putting the centrifuged powder into a drying oven for drying for 8 hours, and exhausting the drying oven for 0-0.5 hour in the drying process;
crushing: and naturally cooling the dried powder, crushing the powder by a crusher within 8 hours, and sealing and packaging to obtain a2, 5-ditert-butylhydroquinone product.
Specifically, the content of D-TBHQ in the prepared 2, 5-ditert-butylhydroquinone product reaches 99.635 percent through gas phase detection, meanwhile, the whiteness of the product is detected to be more than 90 degrees, the D-TBHQ prepared by the embodiment does not turn red or become grey within 1 year, the whiteness is still more than 90 degrees, the product yield is improved by 9.132 percent compared with the original technology, and insoluble substances are qualified, so that the D-TBHQ product prepared by the embodiment has high stability and good quality, and the shelf life reaches 1 year under the normal temperature PE sealing condition.
Example 6
The implementation method for improving the stability of the 2, 5-ditert-butylhydroquinone comprises the following steps:
180g of 2, 5-ditert-butylhydroquinone crude product is added into 95% alcohol with the volume of 2 times, 1.2g of active metal (zinc) is added, after the temperature is raised to 75 ℃ for dissolution, 2.5g of dilute hydrochloric acid with the concentration of 32% is added dropwise, the adding time is 0.5h, and a crude product solution is obtained after the adding is completed;
(2) The crude product solution is subjected to decoloring, concentration, crystallization, centrifugation, drying and crushing in sequence to obtain a 2, 5-ditert-butylhydroquinone product;
Decoloring: adding active carbon into the crude product solution, stirring at 60 ℃ for decoloring for 0.5h, and filtering to obtain a crude product decoloring solution;
concentrating: adding 5g of reducing agent (sodium hydrosulfite) into the decolored crude product decolored solution according to the mass percentage, mixing and stirring, concentrating for 4 hours, and stopping concentrating after 75% alcohol is concentrated to obtain concentrated solution;
Crystallization: cooling and crystallizing after the temperature of the material is reduced to 25 ℃;
And (3) centrifuging: placing the precipitated phase after crystallization in a centrifuge, adding 3 times of alcohol, performing centrifugal washing and throwing, discarding the liquid phase after the centrifugal throwing is finished, taking out the solid phase to form powder, placing the powder in a drying chamber to wait for drying, and placing the powder in the drying chamber to wait for drying for less than 24 hours;
and (3) drying: putting the centrifuged powder into a drying oven for drying, and exhausting the drying oven for 8 hours before 0-0.5 hours in the drying process;
crushing: and naturally cooling the dried powder, crushing the powder by a crusher within 8 hours, and sealing and packaging to obtain a2, 5-ditert-butylhydroquinone product.
Specifically, the content of D-TBHQ in the prepared 2, 5-ditert-butylhydroquinone product reaches 99.635 percent (mass percent), meanwhile, the whiteness of the product is detected to be more than 90 degrees, the D-TBHQ prepared by the embodiment does not turn red or grey within 1 year, the whiteness is still more than 90 degrees, the product yield is improved by 9.532 percent compared with the original technology, and insoluble matters are qualified, so that the D-TBHQ product prepared by the embodiment has high stability and good quality, and the shelf life reaches 1 year under the normal-temperature PE sealing condition.
The technical principle of the present invention is described above in connection with the specific embodiments. The description is made for the purpose of illustrating the general principles of the invention and should not be taken in any way as limiting the scope of the invention. Other embodiments of the invention will be apparent to those skilled in the art from consideration of this specification without undue burden.
Claims (5)
1. A method for improving the stability of 2, 5-ditertbutyl hydroquinone, which is characterized by comprising the following steps:
(1) Dissolving a2, 5-ditert-butylhydroquinone crude product in alcohol added with active metal, heating to 70-75 ℃, dropwise adding dilute acid, and obtaining a crude product solution after the dropwise adding, wherein the mass ratio of the 2, 5-ditert-butylhydroquinone crude product to the active metal to the dilute acid is 1: (0.005-0.007): (0.01-0.015); the active metal is zinc or aluminum;
(2) The crude product solution is subjected to decoloring, concentration, crystallization, centrifugation, drying and crushing in sequence to obtain a 2, 5-ditert-butylhydroquinone product;
The operation method of concentration is as follows: adding 0.5-3% of reducing agent into the decolored crude product decolored solution according to the mass percentage, and concentrating to obtain concentrated solution; the reducing agent is any one of sodium sulfite, sodium hydrosulfite and sodium metabisulfite;
The operation method of the centrifugation is as follows: placing the precipitated phase after crystallization in a centrifuge, adding 3 times of alcohol, performing centrifugal washing and throwing, discarding the liquid phase after centrifugal throwing, and taking out the solid phase to form powder;
the operation method of drying is as follows: and putting the powder obtained by centrifugation into a drying oven for drying for 8-12 hours, and exhausting the drying oven for 0.5-1 hour before the drying process.
2. The method for improving the stability of 2, 5-di-tert-butylhydroquinone according to claim 1, wherein in the step (1), the mass ratio of the active metal to the dilute acid is 1: 2-3.
3. The method for improving the stability of 2, 5-di-tert-butylhydroquinone according to claim 1, wherein in the step (1), the dilute acid is dilute hydrochloric acid or dilute sulfuric acid.
4. The method for improving the stability of 2, 5-di-tert-butylhydroquinone according to claim 1, wherein in the step (2), the decoloring operation is as follows: and adding active carbon into the crude product solution at the temperature of 60-65 ℃ for decoloring for 0.5h, and filtering to obtain the crude product decoloring solution.
5. The method for improving the stability of 2, 5-di-tert-butylhydroquinone according to claim 1, wherein in the step (2), the crystallization operation method comprises the following steps: and after the temperature of the concentrated solution is reduced to 25-35 ℃, separating out crystals.
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