CN112457222A - Preparation method of 2, 7-naphthalene disulfonic acid - Google Patents
Preparation method of 2, 7-naphthalene disulfonic acid Download PDFInfo
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- CN112457222A CN112457222A CN202011310295.4A CN202011310295A CN112457222A CN 112457222 A CN112457222 A CN 112457222A CN 202011310295 A CN202011310295 A CN 202011310295A CN 112457222 A CN112457222 A CN 112457222A
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- naphthalenedisulfonic acid
- naphthalene
- concentrated sulfuric
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- VILFVXYKHXVYAB-UHFFFAOYSA-N naphthalene-2,7-disulfonic acid Chemical compound C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 VILFVXYKHXVYAB-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 80
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000013067 intermediate product Substances 0.000 claims abstract description 19
- 239000011261 inert gas Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000010828 elution Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- FITZJYAVATZPMJ-UHFFFAOYSA-N naphthalene-2,6-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=CC2=CC(S(=O)(=O)O)=CC=C21 FITZJYAVATZPMJ-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000006277 sulfonation reaction Methods 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- APRRQJCCBSJQOQ-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S(O)(=O)=O)=CC2=C1 APRRQJCCBSJQOQ-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- XXOPHNFSAIFMHP-UHFFFAOYSA-N naphthalene-2,7-disulfonic acid;sodium Chemical compound [Na].C1=CC(S(O)(=O)=O)=CC2=CC(S(=O)(=O)O)=CC=C21 XXOPHNFSAIFMHP-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- -1 polydimethylsiloxane Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of 2, 7-naphthalenedisulfonic acid, which comprises the following steps: (1) reacting naphthalene with concentrated sulfuric acid under the protection of inert gas to obtain an intermediate product; (2) reacting the intermediate product obtained in the step (1) with concentrated sulfuric acid under a negative pressure condition to obtain the 2, 7-naphthalenedisulfonic acid; the preparation method improves the conversion rate of naphthalene and the purity of the prepared 2, 7-naphthalenedisulfonic acid by controlling the reaction conditions in different reaction periods, and has low energy consumption and cost and industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of material synthesis, and particularly relates to a preparation method of 2, 7-naphthalenedisulfonic acid.
Background
The 2, 7-naphthalenedisulfonic acid is white and gray crystal, is very easy to absorb water, is an important intermediate in the dye industry, can be used for preparing an important dye intermediate H acid, is mainly applied to cotton, wool, hemp, silk fiber and other industries, and along with the continuous and deep research of various items, the application of the 2, 7-naphthalenedisulfonic acid sodium is more and more extensive.
The traditional method for preparing 2, 7-naphthalene disulfonic acid is to melt refined naphthalene by heating and stirring, a certain amount of concentrated sulfuric acid is dripped after the refined naphthalene is completely melted, and then parameters such as temperature, reaction time and the like are controlled to prepare the 2, 7-naphthalene disulfonic acid. Research shows that in the sulfonation reaction system of naphthalene, under the action of different sulfuric acid concentrations, reaction temperatures and proper catalysts, the sulfonation reaction is reversible, the reaction temperature is increased, and intramolecular rearrangement is easy to occur to change into other isomers.
CN108707094A discloses a method for synthesizing and purifying 2, 6-naphthalenedisulfonic acid and 2, 7-naphthalenedisulfonic acid, which comprises the steps of heating refined naphthalene and concentrated sulfuric acid to carry out sulfonation reaction to generate 2, 6-naphthalenedisulfonic acid and 2, 7-naphthalenedisulfonic acid, adding water to carry out operations such as elution, filtration and washing to obtain a grade-1 2, 6-naphthalenedisulfonic acid filter cake and a grade-1 refined filtrate, and circularly washing the grade-1, 6-naphthalenedisulfonic acid filter cake for 2-4 times to obtain a 2, 6-naphthalenedisulfonic acid product with the purity of more than 99%; the purposes of separating, refining and purifying to obtain high-quality 2, 6-naphthalenedisulfonic acid, improving the recovery rate of the 2, 7-naphthalenedisulfonic acid and reducing the discharge of waste water are achieved. CN101723859A discloses a method for isomerizing 2, 6-naphthalenedisulfonic acid into 2, 7-naphthalenedisulfonic acid, which comprises adding 1 part by weight of a 2, 6-naphthalenedisulfonic acid solution with a mass concentration of 50-100%, 0.5-2 parts by weight of concentrated sulfuric acid with a mass concentration of 98% and a super strong acid catalyst accounting for 0.05-5% of the total weight of the 2, 6-naphthalenedisulfonic acid solution into a reaction kettle, and reacting at 160-220 ℃ for 2-10 hours to obtain a sulfonated liquid with the content of the 2, 7-naphthalenedisulfonic acid being greater than 64%. The method fully utilizes the unsmooth 2, 6-naphthalenedisulfonic acid in the market, prepares the marketable 2, 7-naphthalenedisulfonic acid and downstream products thereof in the market through intramolecular rearrangement, meets the requirements of the market and the society, reduces the environmental pollution and improves the economic benefit. Through research, Liudong et al also find that naphthalene, concentrated sulfuric acid and fuming acid can generate 2, 6-naphthalenedisulfonic acid and 2, 7-naphthalenedisulfonic acid under certain conditions, and a filter cake mainly containing the 2, 6-naphthalenedisulfonic acid and a mother liquor mainly containing the 2, 7-naphthalenedisulfonic acid are obtained through water dissolution, wherein the conversion rate of the 2, 7-naphthalenedisulfonic acid is 58%. (see "study of sulfonation reaction history of naphthalene in concentrated sulfuric acid", dye and stain, vol 54, sixth of 2017). However, most of the preparation methods used in the prior art have the problems of high reaction temperature and low conversion rate, the high reaction temperature can cause high energy consumption of the reaction, and the raw material naphthalene is easily oxidized and carbonized in the reaction process, so that the utilization rate of the naphthalene is too low, the reaction cost is increased, the product purity is insufficient, and the like.
Therefore, the development of a preparation method with high naphthalene utilization rate, low reaction energy consumption and low cost to prepare the high-purity 2, 7-naphthalenedisulfonic acid is of great significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of 2, 7-naphthalenedisulfonic acid, which improves the conversion rate of naphthalene and the generation purity of the 2, 7-naphthalenedisulfonic acid by controlling reaction conditions in different reaction periods, and has low energy consumption, low cost and wide industrial application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of 2, 7-naphthalenedisulfonic acid, which comprises the following steps:
(1) reacting naphthalene with concentrated sulfuric acid under the protection of inert gas to obtain an intermediate product;
(2) and (2) reacting the intermediate product obtained in the step (1) with concentrated sulfuric acid under a negative pressure condition to obtain the 2, 7-naphthalenedisulfonic acid.
The preparation method of the 2, 7-naphthalenedisulfonic acid provided by the invention comprises two steps: firstly, naphthalene and concentrated sulfuric acid are reacted under the protection of inert gas to obtain an intermediate product, wherein the reaction formula is shown as formula I:
the first-step sulfonation reaction is carried out under the protective atmosphere of inert gas, so that the problem of oxidative carbonization of naphthalene in the high-temperature reaction process is avoided, the utilization rate of the naphthalene raw material is improved, and the reduction of the use amount of concentrated sulfuric acid is facilitated, so that the waste gas discharge amount is reduced, and the environmental pressure is reduced; then, the intermediate product is continuously reacted with concentrated sulfuric acid under the negative pressure condition to obtain the 2, 7-naphthalenedisulfonic acid, wherein the reaction formula is shown as a formula II:
the second-step sulfonation reaction of the intermediate product and concentrated sulfuric acid is reversible, and vacuum dehydration is performed under the negative pressure condition, so that the reversible reaction is favorably carried out in the forward direction, the balance of the reversible reaction can be moved in the forward direction, the generation rate of the 2, 7-naphthalenedisulfonic acid is improved, and the conversion rate of naphthalene is further improved.
Preferably, the molar ratio of naphthalene to concentrated sulfuric acid in step (1) is 1 (1.15-3), such as 1:1.16, 1:1.17, 1:1.18, 1:1.19, 1:1.2, 1:1.21, 1:1.22, 1:1.23, 1:1.24, 1:1.25, 1:1.26, 1:1.27, 1:1.28, or 1: 1.29.
Preferably, the naphthalene comprises industrial naphthalene and/or refined naphthalene.
Preferably, the concentrated sulfuric acid has a concentration of greater than 90%, such as 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, and the specific values therebetween are not exhaustive for the invention and are included for the sake of brevity and conciseness.
Preferably, the inert gas in step (1) comprises any one of nitrogen, helium, neon, argon or krypton or a combination of at least two of the same.
Preferably, the reaction temperature in step (1) is 80-95 ℃, such as 81 ℃, 82 ℃, 83 ℃, 84 ℃, 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃ or 94 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction time of step (1) is 150-180 min, such as 152min, 154min, 156min, 158min, 160min, 162min, 164min, 166min, 168min, 170min, 172min, 174min, 176min or 178min, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the molar ratio of the intermediate product in the step (2) to the concentrated sulfuric acid in the step (2) is 1 (2-2.5), such as 1:2.21, 1:2.22, 1:2.23, 1:2.24, 1:2.25, 1:2.26, 1:2.28, 1:2.3, 1:32, 1:2.34, 1:2.36, 1:2.38, 1:2.4, 1:2.42, 1:2.44, 1:2.46, or 1: 2.48.
Preferably, the negative pressure in step (2) is 10 to 100Pa, such as 15Pa, 20Pa, 25Pa, 30Pa, 35Pa, 40Pa, 45Pa, 50Pa, 55Pa, 60Pa, 65Pa, 70Pa, 75Pa, 80Pa, 85Pa, 90Pa or 95Pa, and the specific values therebetween are not exhaustive, and for brevity and conciseness, the invention does not provide an exhaustive list of the specific values included in the range.
Preferably, the reaction temperature in step (2) is 135-145 ℃, for example, 136 ℃, 137 ℃, 138 ℃, 139 ℃, 140 ℃, 141 ℃, 142 ℃, 143 ℃ or 144 ℃, and the specific values therebetween are limited by space and for brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction time in step (2) is 1 to 10 hours, such as 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, 6 hours, 6.5 hours, 7 hours, 7.5 hours, 8 hours, 8.5 hours, 9 hours or 9.5 hours, and the specific values therebetween are limited by space and for brevity, and the invention is not exhaustive of the specific values included in the range.
Preferably, the reaction in step (2) further comprises a post-treatment step after the reaction is completed.
Preferably, the post-treatment comprises the steps of cooling, adding water to control acidity, elution and filtration.
Preferably, the cooling time is 50 to 90 ℃, such as 52 ℃, 54 ℃, 56 ℃, 58 ℃, 60 ℃, 62 ℃, 64 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃, 82 ℃, 84 ℃, 86 ℃ or 88 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive of the specific values included in the ranges.
Preferably, the acidity is 50-90%, such as 52%, 54%, 56%, 58%, 60%, 62%, 64%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, or 88%, and specific points therebetween, for brevity and conciseness, the invention is not exhaustive of the specific points included in the ranges.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) reacting naphthalene with a molar ratio of 1 (1.15-3) and concentrated sulfuric acid with a concentration of more than 90% for 150-180 min at a temperature of 80-95 ℃ under the protection of inert gas to obtain an intermediate product;
(2) reacting the intermediate product with a molar ratio of 1 (2-2.5) with concentrated sulfuric acid for 150-10 h at a temperature of 135-145 ℃ and a negative pressure of 10-100 Pa, cooling to 50-90 ℃, adding water to control the acidity to be 50-90%, dissolving out, and filtering to obtain the 2, 7-naphthalenedisulfonic acid.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of the 2, 7-naphthalenedisulfonic acid, naphthalene and concentrated sulfuric acid are reacted under the protection of inert gas to obtain an intermediate product, the conversion rate of the naphthalene is improved under the protection of the inert gas, and the cost is saved; then, reacting the intermediate product with concentrated sulfuric acid under a negative pressure condition to obtain the 2, 7-naphthalenedisulfonic acid, and performing the second step of reaction under the negative pressure condition is favorable for improving the generation rate of the 2, 7-naphthalenedisulfonic acid; specifically, the naphthalene content in the reaction liquid obtained by the preparation method provided by the invention is 0.27-0.94%, and is reduced by 46-2133% compared with the naphthalene content in the reaction liquid obtained by the preparation method provided by the prior art, so that the naphthalene utilization rate of the preparation method provided by the invention is high; secondly, the content of the 2, 6-naphthalenedisulfonic acid and the content of the 2, 7-naphthalenedisulfonic acid in the product obtained by the preparation method provided by the invention are respectively 23.52-32.92% and 67.85-71.96%, compared with the product obtained by the preparation method provided by the prior art, the content of the 2, 6-naphthalenedisulfonic acid is reduced by 2-71%, and the content of the 2, 7-naphthalenedisulfonic acid is improved by 55-86%, so that the purity of the 2, 7-naphthalenedisulfonic acid prepared by the preparation method provided by the invention is improved; and the preparation method has low energy consumption and low cost, and has industrial large-range application prospect.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
A preparation method of 2, 7-naphthalene disulfonic acid specifically comprises the following steps:
(1) heating 1mol of industrial naphthalene to 80 ℃, after completely melting, slowly adding 1.15mol of concentrated sulfuric acid with the concentration of 98%, heating to 90 ℃ under the protection of nitrogen, and reacting for 150min to obtain an intermediate product;
(2) adding 2mol of 98% concentrated sulfuric acid into the intermediate product obtained in the step (1), vacuumizing to enable the negative pressure of the reaction to be 10Pa, heating to 135 ℃, cooling to 50 ℃ after reacting for 6 hours, adding water to control the acidity to be 50mgKOH/g, and carrying out elution and filtration to obtain the 2, 7-naphthalenedisulfonic acid.
Example 2
A preparation method of 2, 7-naphthalenedisulfonic acid, which is different from the example 1 only in that the 98% concentrated sulfuric acid in the step (1) is added in an amount of 1.3mol, and other components, amounts and process parameters are the same as those in the example 1, thereby obtaining the 2, 7-naphthalenedisulfonic acid.
Example 3
A preparation method of 2, 7-naphthalenedisulfonic acid, which is different from the example 1 only in that the 98% concentrated sulfuric acid in the step (1) is added in an amount of 1.55mol, and other components, amounts and process parameters are the same as those in the example 1, thereby obtaining the 2, 7-naphthalenedisulfonic acid.
Example 4
The preparation method of 2, 7-naphthalenedisulfonic acid is different from the example 1 only in that the reaction time of the step (1) is 180min, and other components, the using amount and the process parameters are the same as those of the example 1, so that the 2, 7-naphthalenedisulfonic acid is obtained.
Example 5
The preparation method of the 2, 7-naphthalenedisulfonic acid is different from the example 1 only in that the temperature in the step (1) is increased to 95 ℃ under the protection of nitrogen, and other components, the using amount and the process parameters are the same as those in the example 1, so that the 2, 7-naphthalenedisulfonic acid is obtained.
Example 6
A preparation method of 2, 7-naphthalenedisulfonic acid, which is different from the example 1 only in that the 98% concentrated sulfuric acid in the step (2) is added in an amount of 2.5mol, and other components, amounts and process parameters are the same as those in the example 1, thereby obtaining the 2, 7-naphthalenedisulfonic acid.
Example 7
A preparation method of 2, 7-naphthalenedisulfonic acid, which is different from the example 1 only in that the 98% concentrated sulfuric acid in the step (2) is added in an amount of 1.5mol, and other components, amounts and process parameters are the same as those in the example 1, thereby obtaining the 2, 7-naphthalenedisulfonic acid.
Example 8
A preparation method of 2, 7-naphthalenedisulfonic acid, which is different from the example 1 only in that the 98% concentrated sulfuric acid in the step (2) is added in an amount of 3mol, and other components, amounts and process parameters are the same as those in the example 1, thereby obtaining the 2, 7-naphthalenedisulfonic acid.
Example 9
The preparation method of 2, 7-naphthalenedisulfonic acid is different from the example 1 only in that the negative pressure of the reaction in the step (2) is 100Pa, and other components, the use amounts and the process parameters are the same as those in the example 1, so that the 2, 7-naphthalenedisulfonic acid is obtained.
Example 10
The preparation method of the 2, 7-naphthalenedisulfonic acid is different from the example 1 only in that the temperature in the step (2) is increased to 145 ℃ under the protection of nitrogen, and other components, the using amount and the process parameters are the same as those in the example 1, so that the 2, 7-naphthalenedisulfonic acid is obtained.
Example 11
The preparation method of 2, 7-naphthalenedisulfonic acid is different from the example 1 only in that the reaction time of the step (2) is 10 hours, and other components, the using amounts and the process parameters are the same as those of the example 1, so that the 2, 7-naphthalenedisulfonic acid is obtained.
Comparative example 1
A method for preparing 2, 7-naphthalenedisulfonic acid, which is different from example 1 only in that the nitrogen gas in step (1) is replaced with air and the other components, the amounts and the process parameters are the same as those in example 1 to obtain the 2, 7-naphthalenedisulfonic acid.
Comparative example 2
A method for preparing 2, 7-naphthalenedisulfonic acid, which is different from example 1 only in that the negative pressure in step (2) is replaced by atmospheric pressure, and the other components, the amounts and the process parameters are the same as those in example 1 to obtain the 2, 7-naphthalenedisulfonic acid.
Comparative example 3
A preparation method of 2, 7-naphthalenedisulfonic acid, which is different from the embodiment 1 only in that nitrogen in the step (1) is replaced by air, the negative pressure in the step (2) is replaced by atmospheric pressure, and other components, the amounts and process parameters are the same as those in the embodiment 1, thereby obtaining the 2, 7-naphthalenedisulfonic acid.
And (3) performance testing:
naphthalene content in the reaction liquid, 2, 6-naphthalenedisulfonic acid content and 2, 7-naphthalenedisulfonic acid content in the product:
testing an instrument: gas chromatography (north branch 3420) column was used: HP-5 (polydimethylsiloxane capillary column, chromatography column model 30m × 0.25mm × 0.25 μm;
and (3) testing conditions are as follows: the sample inlet temperature is 240 ℃, the detector temperature is 250 ℃, the initial column temperature is 60 ℃ and is kept for 1min, then the temperature is increased to 220 ℃ at the rate of 10 ℃/min and is kept for 15min, the carrier gas flow rate is 1.0mL/min, and the split ratio is 30: 1; the sample injection amount is 1mL by headspace sampling method.
The testing steps are as follows: preparing a standard working solution: respectively weighing 0.1g of naphthalene, 2, 6-naphthalenedisulfonic acid and 2, 7-naphthalenedisulfonic acid, respectively dissolving the two in a 50mL volumetric flask by using ethyl acetate as a solvent, metering the volume to the scale, and shaking up; ② 0.02mL of standard solution is injected into a 20mL headspace bottle, the balance is carried out for 1h at 90 ℃, and 1mL of sample is injected; and (4) determining the quality by using retention time, determining the peak area, and finally obtaining a standard curve by using the peak area A as a vertical coordinate and the corresponding concentration as a horizontal coordinate, and calculating the corresponding content according to the standard curve.
The reaction solutions and products obtained in the preparation methods described in examples 1 to 11 and comparative examples 1 to 3 were tested according to the above test methods, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1: the preparation method of the 2, 7-naphthalenedisulfonic acid provided by the invention has the advantages that the naphthalene raw material has high utilization rate, and the prepared 2, 7-naphthalenedisulfonic acid has high content; specifically, the naphthalene content in the reaction liquid obtained by the preparation method provided in the embodiments 1 to 11 is 0.27 to 0.94%, which is reduced by 46 to 2133% compared with the naphthalene content in the reaction liquid obtained by the preparation method provided in the prior art (comparative examples 1 to 3), and it is proved that the naphthalene utilization rate of the preparation method provided by the invention is high; the content of the 2, 6-naphthalenedisulfonic acid and the content of the 2, 7-naphthalenedisulfonic acid in the products obtained by the preparation methods provided in examples 1 to 11 are 23.52 to 32.92% and 67.85 to 71.96%, respectively, and compared with the content of the 2, 6-naphthalenedisulfonic acid in the products obtained by the preparation methods provided in the prior art (comparative examples 1 to 3), the content of the 2, 7-naphthalenedisulfonic acid in the products obtained by the preparation methods provided in the prior art (comparative examples 1 to 3) is reduced by 2 to 71%, and compared with the content of the 2, 7-naphthalenedisulfonic acid in the products obtained by the preparation methods provided in the prior art (comparative examples 1 to 3), the content of the 2, 7-naphthalenedisulfonic acid is increased by 55 to 86%, which further proves that the 2, 7-naphthalenedisulfonic.
The applicant states that the present invention is illustrated by the above examples as a process for the preparation of 2, 7-naphthalenedisulfonic acid, but the present invention is not limited to the above process steps, i.e., it is not meant to imply that the present invention must rely on the above process steps to be practiced. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which fall within the scope and disclosure of the present invention, are contemplated.
Claims (10)
1. A preparation method of 2, 7-naphthalenedisulfonic acid is characterized by comprising the following steps:
(1) reacting naphthalene with concentrated sulfuric acid under the protection of inert gas to obtain an intermediate product;
(2) and (2) reacting the intermediate product obtained in the step (1) with concentrated sulfuric acid under a negative pressure condition to obtain the 2, 7-naphthalenedisulfonic acid.
2. The preparation method according to claim 1, wherein the molar ratio of naphthalene to concentrated sulfuric acid in the step (1) is 1 (1.15-1.3);
preferably, the naphthalene comprises industrial naphthalene and/or refined naphthalene;
preferably, the concentrated sulfuric acid concentration in step (1) and step (2) is independently greater than 90%.
3. The method according to claim 1 or 2, wherein the inert gas in the step (1) comprises any one of nitrogen, helium, neon, argon or krypton, or a combination of at least two thereof.
4. The method according to any one of claims 1 to 3, wherein the reaction temperature in step (1) is 80 to 95 ℃;
preferably, the reaction time in the step (1) is 150-180 min.
5. The method according to any one of claims 1 to 4, wherein the molar ratio of the intermediate product in step (2) to the concentrated sulfuric acid in step (2) is 1 (2 to 2.5).
6. The method according to any one of claims 1 to 5, wherein the negative pressure in the step (2) is 10 to 100 Pa.
7. The method according to any one of claims 1 to 6, wherein the temperature of the reaction in the step (2) is 135 to 145 ℃.
8. The method according to any one of claims 1 to 7, wherein the reaction time in the step (2) is 1 to 10 hours.
9. The method according to any one of claims 1 to 8, wherein the reaction of step (2) is completed and then a post-treatment step is further included;
preferably, the post-treatment comprises the steps of cooling, adding water to control acidity, elution and filtration;
preferably, the cooling temperature is 50-90 ℃;
preferably, the acidity is 50 to 90 mgKOH/g.
10. The method according to any one of claims 1 to 9, characterized by comprising the steps of:
(1) reacting naphthalene with a molar ratio of 1 (1.15-3) and concentrated sulfuric acid with a concentration of more than 90% for 150-180 min at a temperature of 80-95 ℃ under the protection of inert gas to obtain an intermediate product;
(2) reacting the intermediate product with a molar ratio of 1 (2-2.5) with concentrated sulfuric acid for 1-10 h at a temperature of 135-145 ℃ and a negative pressure of 10-100 Pa, cooling to 50-90 ℃, adding water to control the acidity to be 50-90%, dissolving out, and filtering to obtain the 2, 7-naphthalenedisulfonic acid.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58180466A (en) * | 1982-04-14 | 1983-10-21 | Nippon Soda Co Ltd | Preparation of naphthalenesulfonic acid |
| JPH11292838A (en) * | 1998-04-03 | 1999-10-26 | Adchemco Kk | Production of beta-naphthalenesulfonic acid |
| CN103694149A (en) * | 2013-11-28 | 2014-04-02 | 枣庄市泰瑞精细化工有限公司 | Method for producing 2,7-sodium naphthalene disulfonate by using reaction mother liquor of 2-naphthalene sulfonic acid |
-
2020
- 2020-11-20 CN CN202011310295.4A patent/CN112457222A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58180466A (en) * | 1982-04-14 | 1983-10-21 | Nippon Soda Co Ltd | Preparation of naphthalenesulfonic acid |
| JPH11292838A (en) * | 1998-04-03 | 1999-10-26 | Adchemco Kk | Production of beta-naphthalenesulfonic acid |
| CN103694149A (en) * | 2013-11-28 | 2014-04-02 | 枣庄市泰瑞精细化工有限公司 | Method for producing 2,7-sodium naphthalene disulfonate by using reaction mother liquor of 2-naphthalene sulfonic acid |
Non-Patent Citations (1)
| Title |
|---|
| WILFRED L.F.ARMAREGO,CHRISTINA LI LIN CHAI: "《Purification of Laboratory Chemicals Sixth Edition》", 31 December 2009 * |
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