CN110302793B - Catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate and application thereof - Google Patents
Catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 88
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 29
- 239000011734 sodium Substances 0.000 title claims abstract description 29
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 18
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 18
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims abstract description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000001354 calcination Methods 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 12
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims description 12
- HTXMGVTWXZBZNC-UHFFFAOYSA-N 3,5-bis(methoxycarbonyl)benzenesulfonic acid Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(S(O)(=O)=O)=C1 HTXMGVTWXZBZNC-UHFFFAOYSA-N 0.000 claims description 11
- 238000011068 loading method Methods 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229920006332 epoxy adhesive Polymers 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000005469 granulation Methods 0.000 claims description 7
- 230000003179 granulation Effects 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 abstract description 14
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 6
- 230000035484 reaction time Effects 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000003213 activating effect Effects 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 230000003472 neutralizing effect Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 230000032050 esterification Effects 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000370 mercury sulfate Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- C07C303/32—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of salts of sulfonic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate, a preparation method and application thereof, wherein the catalyst comprises a composite carrier and an active component, the composite carrier comprises a diatomite carrier and a rho-alumina carrier, and the mass-to-weight ratio of the diatomite carrier to the rho-alumina carrier is 1: 1.8-2.3; the active component comprises dibutyltin oxide and copper chloride, and the mixing mass ratio of the dibutyltin oxide to the copper chloride is 1: 0.7 to 1; the mass ratio of the active component to the composite carrier of the catalyst is 5-10: 100. the catalyst is adopted to catalyze and synthesize the m-phthalic acid dimethyl ester-5-sodium sulfonate, so that the sulfonation reaction temperature can be reduced, the sulfonation reaction time can be shortened, the reaction yield and purity can be improved, the synthesis cost of the three monomers can be reduced, meanwhile, the catalyst is high in catalysis efficiency, the recycling frequency can be up to 50 times, and the utilization efficiency of the catalyst can be greatly improved.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate (commonly known as a tri-monomer and abbreviated as SIPM), a preparation method and application thereof.
Background
The method for synthesizing the tri-monomer by using the isophthalic acid as the starting raw material basically comprises the following steps of: (1) a sulfonic acid crystallization method, namely sulfonating isophthalic acid by using sulfur trioxide or fuming sulfuric acid, then diluting a sulfonation mother liquor by using ice water until the mass fraction of sulfuric acid is 50-70%, so that sulfonic acid is crystallized and separated out, removing redundant waste acid, esterifying by using excessive methanol, and then neutralizing and refining to prepare SIPM; (2) sulfonating chlorosulfonic acid, sulfonating with chlorosulfonic acid as sulfonating agent, neutralizing, filtering, separating, oven drying to obtain sodium m-phthalate-5-sulfonate, esterifying, neutralizing, and refining to obtain SIPM; (3) the fuming sulfuric acid 'one-pot' process is to sulfonate isophthalic acid with fuming sulfuric acid of different concentration, to obtain sulfonated matter, to esterify directly with residual waste acid as catalyst, to neutralize and to refine to obtain SIPM. (4) The esterification sulfonation method comprises the steps of firstly adding methanol into isophthalic acid for esterification to prepare dimethyl isophthalate, then mixing the dimethyl isophthalate with the isophthalic acid, sulfonating the mixture by sulfur trioxide (S03) or fuming sulfuric acid, and then esterifying, neutralizing and refining the mixture of dimethyl isophthalate-monosulfonic acid and isophthalic acid-monosulfonic acid to obtain the SIPM. In the SIPM synthesis process, sulfonation reaction is a key step, and in the esterification sulfonation method, two carboxyl groups-COOH in the molecular structure of isophthalic acid are electron-withdrawing groups, so that the isophthalic acid has a passivation effect on benzene rings, and the sulfonation reaction is difficult.
Chinese patent CN109180538 discloses a production method for improving the yield of m-phthalic acid-5-sulfonic acid for synthesizing three monomers, which changes the proportion of raw materials, and reduces the loss of sulfur trioxide and improves the yield of sulfonation reaction by adding fuming sulfuric acid in batches and matching with three-stage heating reaction. However, this process has a high reaction temperature, and the operation is complicated because the temperature is strictly controlled in three stages.
CN102633693 discloses a method for synthesizing sodium dimethyl isophthalate-5-sulfonate, wherein the sulfonation reaction is carried out by adjusting the reaction temperature and sequentially adding three different catalysts, namely cadmium sulfate, SiO2 and mercury sulfate, so as to promote the process of the sulfonation reaction, but a large amount of heavy metal catalyst cannot be reasonably recovered, so that not only is the water body polluted, but also the cost is increased.
Disclosure of Invention
Aiming at the problems in the prior art in China, the invention deeply researches the prior process to form a new synthesis process so as to achieve the aims of improving the yield and the product purity of the sulfonation reaction, reducing the temperature of the sulfonation reaction and shortening the reaction time.
In order to solve the technical problems, the invention adopts the following technical scheme:
a catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate is characterized by comprising a composite carrier and an active component;
the composite carrier comprises a diatomite carrier and a rho-alumina carrier, wherein the mass ratio of the diatomite carrier to the rho-alumina carrier is 1: 1.8-2.3;
the active component comprises dibutyltin oxide and copper chloride, and the mass ratio of the dibutyltin oxide to the copper chloride is 1: 0.7 to 1;
the mass ratio of the active component to the composite carrier of the catalyst is 5-10: 100, respectively;
the specific surface area of the supported catalyst is 700-1000 m 2/g.
A preparation method of a catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate is characterized by comprising the steps of preparing a composite carrier and loading active components;
the active component loading comprises calcination and is characterized in that the calcination temperature is 200-280 ℃, and the calcination time is 4-6 h;
the preparation of the composite carrier comprises the preparation of a diatomite carrier, wherein the diatomite carrier is fully washed by ultrapure water, dried, placed in a muffle furnace, burned for 4 hours at 650 ℃, and then cooled to 100 ℃ for activation for 2 hours;
the active component loading comprises ball milling, the rotating speed of the ball mill is 400-;
the active component loading comprises granulation and is characterized in that the addition amount of the epoxy adhesive accounts for 2-5% of the weight of the catalyst, and the particle size of the particles is less than or equal to 200 meshes.
The application of the catalyst for synthesizing the dimethyl isophthalate-5-sodium sulfonate is characterized by comprising the steps of feeding, first-stage heating reaction, second-stage heating reaction and post-treatment;
the weight ratio of the dimethyl isophthalate to 65% fuming sulfuric acid is 1.320-1.356: 1; the adding amount of the catalyst is 20-35% of dimethyl isophthalate by weight;
the first-stage heating reaction is to heat the temperature of the sulfonation kettle from normal temperature to 90-100 ℃ within 20-30 minutes, and to react for 60 minutes;
the second-stage heating reaction, namely heating the sulfonation kettle to 115-120 ℃ within 10-15 minutes, and preserving the heat for 50-80 minutes at the temperature;
the post-treatment comprises filtration and drying and recycling of filter cakes; and adding 20% NaOH solution into the filtrate to adjust the pH value to 6.5-7.5, keeping the temperature rise to be not more than 15 ℃, dropwise adding to increase the stirring speed, and quickly continuing to stir for 60-65 minutes.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the reaction temperature is reduced, the reaction temperature is 90-120 ℃ by adopting the technical scheme of the invention, and the reaction temperature in the prior art is at least over 145 ℃ and even exceeds 160 ℃.
2. Improve the reaction purity and yield
The purity of the isophthalic acid dimethyl ester-5-sulfonic acid in the sulfonated material is detected and analyzed by adopting a liquid chromatography, the purity of the isophthalic acid dimethyl ester-5-sulfonic acid is 99.14-99.67%, and the yield is 99.12-99.42%.
3. Shortening sulfonation reaction time
The sulfonation reaction time is 110min-140min, the reaction time of the existing process is more than 5 hours, and the industrial consumption cost is reduced.
4. Reduce the unit consumption of fuming sulfuric acid, reduce the loss and reduce the cost
The amount of oleum is reduced, and the temperature is reduced to reduce the thermal escape loss value of SO 3. In addition, compared with the prior art, the amount of NaOH is reduced by 11 percent in the post-treatment process, the amount of wastewater generated by post-treatment is also reduced, and the energy consumption and the wastewater treatment cost are reduced.
5. The catalyst has high catalytic efficiency, can be recycled, is clean and has no pollution
The catalyst can be recycled after high-temperature calcination, the application frequency reaches 50 times, the service life of the catalyst is long, the loading effect is good, the specific surface area of the catalyst reaches 900-1000 m2/g, and the overflow concentration of heavy metals is very low.
6. The tri-monomer product prepared by the catalyst of the invention has excellent performance
The acid value of the tri-monomer prepared by the catalyst of the invention is not more than 0.28mgKOH/g, the saponification value is 378.13-378.75mgKOH/g, the sulfate radical content is not more than 52mg/kg, and the water content is less than 0.2 wt%.
The specific implementation mode is as follows:
example 1 catalyst for synthesis of dimethyl isophthalate-5-sodium sulfonate and use thereof
Catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate
The catalyst comprises a composite carrier and an active component; the mass ratio of the active component to the composite carrier is 5: 100;
the composite carrier comprises a diatomite carrier and a rho-alumina carrier, wherein the mass ratio of the diatomite carrier to the rho-alumina carrier is 1: 1.8;
the active component comprises dibutyltin oxide and copper chloride, and the mass ratio of the dibutyltin oxide to the copper chloride is 1: 0.8.
The preparation method of the catalyst comprises the following steps:
(1) preparation of composite Carrier
And mixing and stirring the diatomite carrier and the rho-alumina carrier according to the mass ratio of 1:1.8 to obtain the composite carrier.
The preparation method of the diatomite carrier comprises the following steps: fully washing the diatomite with ultrapure water, drying in the air, putting the diatomite in a muffle furnace, firing for 4 hours at 650 ℃, and then activating for 2 hours at 100 ℃ to obtain a diatomite carrier after activation;
(2) active ingredient loading
A. Ball mill
Mixing dibutyltin oxide and copper chloride powder in proportion, adding the mixture into a ball mill, adding a composite carrier, mixing and grinding at the rotating speed of 400r/min for 5 hours to obtain a mixture of an active component and the composite carrier;
B. granulating
Adding a mixture of the active component and the composite carrier into a granulator, adding 2% of epoxy adhesive for granulation treatment, wherein the granularity of the mixed fine materials is less than or equal to 200 meshes, and obtaining catalyst prefabricated particles;
C. calcination of
And finally, calcining the catalyst preformed particles at the temperature of 200 ℃ for 4 hours to obtain the composite carrier catalyst.
Secondly, application of the catalyst in synthesis of dimethyl isophthalate-5-sulfonic acid
Charging
Putting fuming sulfuric acid into a sulfonation kettle, starting stirring, dropwise adding dimethyl isophthalate into the sulfonation kettle, and adding a catalyst, wherein the weight ratio of dimethyl isophthalate: 65% oleum = 1.320: 1, catalyst: dimethyl isophthalate =20: 100;
② first stage heating reaction
The temperature of the sulfonation kettle is raised from normal temperature to 90 ℃ within 20 minutes, and the reaction is carried out for 60 minutes;
third step of temperature rising reaction
Carrying out the second-stage heating after the first-stage reaction is carried out for 60 minutes, heating the sulfonation kettle to 115 ℃ in 10 minutes, and carrying out heat preservation for 60 minutes at the temperature;
fourthly, post-treatment
After the reaction is finished, the catalyst is filtered and recovered, and the catalyst can be reused after being dried. Adding a large amount of water into the reacted materials, cooling to room temperature, adding 20% NaOH solution to adjust the pH, adjusting the adding speed to ensure that the temperature rise does not exceed 15 ℃, stopping adding alkali when the pH is 6.5, increasing the stirring speed, and quickly continuing stirring for 60 minutes.
And filtering, centrifugally dewatering, dissolving and decolorizing, crystallizing and purifying, drying and the like the materials after the neutralization reaction to prepare the sodium dimethyl isophthalate-5-sulfonate.
The quality indexes of the prepared product are shown in table 1:
example 2 catalyst for synthesis of dimethyl isophthalate-5-sodium sulfonate and use thereof
Catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate
The catalyst comprises a composite carrier and an active component; the mass ratio of the active component to the composite carrier is 8: 100;
the composite carrier comprises a diatomite carrier and a rho-alumina carrier, wherein the mass ratio of the diatomite carrier to the rho-alumina carrier is 1: 2;
the active component comprises dibutyltin oxide and copper chloride, and the mass ratio of the dibutyltin oxide to the copper chloride is 1: 0.8;
the preparation method of the catalyst comprises the following steps:
(1) preparation of composite Carrier
And mixing and stirring the diatomite carrier and the rho-alumina carrier according to the mass ratio of 1:2 to obtain the composite carrier.
The preparation method of the diatomite carrier comprises the following steps: fully washing the diatomite with ultrapure water, drying in the air, putting the diatomite in a muffle furnace, firing for 4 hours at 650 ℃, and then activating for 2 hours at 100 ℃ to obtain a diatomite carrier after activation;
(2) active ingredient loading
A. Ball mill
Mixing dibutyltin oxide and copper chloride powder in proportion, adding the mixture into a ball mill, adding a composite carrier, mixing and grinding at the rotating speed of 400r/min for 7 hours to obtain a mixture of an active component and the composite carrier;
B. granulating
Adding a mixture of the active component and the composite carrier into a granulator, adding 2% of epoxy adhesive for granulation treatment, wherein the granularity of the mixed fine materials is less than or equal to 200 meshes, and obtaining catalyst prefabricated particles;
C. calcination of
And finally, calcining the catalyst preformed particles at the temperature of 250 ℃ for 4 hours to obtain the composite carrier catalyst.
Secondly, application of the catalyst in synthesis of dimethyl isophthalate-5-sulfonic acid
Charging
Putting fuming sulfuric acid into a sulfonation kettle, starting stirring, dropwise adding dimethyl isophthalate into the sulfonation kettle, and adding a catalyst, wherein the weight ratio of dimethyl isophthalate: 65% oleum = 1.335: 1, catalyst: dimethyl isophthalate =25: 100;
② first stage heating reaction
The temperature of the sulfonation kettle is raised from normal temperature to 94 ℃ within 23 minutes, and the reaction is carried out for 60 minutes;
third step of temperature rising reaction
Carrying out the second-stage heating after the first-stage reaction is carried out for 60 minutes, heating the sulfonation kettle to 115 ℃ in 10 minutes, and preserving the heat for 80 minutes at the temperature;
fourthly, post-treatment
After the reaction is finished, the catalyst is filtered and recovered, and the catalyst can be reused after being dried. Adding a large amount of water into the reacted materials, cooling to room temperature, adding 20% NaOH solution to adjust the pH, adjusting the adding speed to ensure that the temperature rise does not exceed 15 ℃, stopping adding alkali when the pH is 6.8, increasing the stirring speed, and quickly continuing stirring for 60 minutes.
And filtering, centrifugally dewatering, dissolving and decolorizing, crystallizing and purifying, drying and the like the materials after the neutralization reaction to prepare the sodium dimethyl isophthalate-5-sulfonate.
The quality indexes of the prepared product are shown in table 2:
example 3 catalyst for synthesis of dimethyl isophthalate-5-sodium sulfonate and use thereof
Catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate
The catalyst comprises a composite carrier and an active component; the mass ratio of the active component to the composite carrier is 9: 100;
the composite carrier comprises a diatomite carrier and a rho-alumina carrier, wherein the mass ratio of the diatomite carrier to the rho-alumina carrier is 1: 2.3;
the active component comprises dibutyltin oxide and copper chloride, and the mass ratio of the dibutyltin oxide to the copper chloride is 1: 0.9;
the preparation method of the catalyst comprises the following steps:
(1) preparation of composite Carrier
And mixing and stirring the diatomite carrier and the rho-alumina carrier according to the mass ratio of 1:2.3 to obtain the composite carrier.
The preparation method of the diatomite carrier comprises the following steps: fully washing the diatomite with ultrapure water, drying in the air, putting the diatomite in a muffle furnace, firing for 4 hours at 650 ℃, and then activating for 2 hours at 100 ℃ to obtain a diatomite carrier after activation;
(2) active ingredient loading
A. Ball mill
Mixing dibutyltin oxide and copper chloride powder in proportion, adding the mixture into a ball mill, adding a composite carrier, mixing and grinding at the rotating speed of 500r/min for 6 hours to obtain a mixture of an active component and the composite carrier;
B. granulating
Adding a mixture of the active component and the composite carrier into a granulator, adding 3% of epoxy adhesive for granulation treatment, wherein the granularity of the mixed fine materials is less than or equal to 200 meshes, and obtaining catalyst prefabricated particles;
C. calcination of
And finally, calcining the catalyst preformed particles at 280 ℃ for 5 hours to obtain the composite supported catalyst.
Secondly, application of the catalyst in synthesis of dimethyl isophthalate-5-sulfonic acid
Charging
Putting fuming sulfuric acid into a sulfonation kettle, starting stirring, dropwise adding dimethyl isophthalate into the sulfonation kettle, and adding a catalyst, wherein the weight ratio of dimethyl isophthalate: 65% oleum = 1.356: 1, catalyst: dimethyl isophthalate =25: 100;
② first stage heating reaction
The temperature of the sulfonation kettle is raised from normal temperature to 100 ℃ within 25 minutes, and the reaction is carried out for 60 minutes;
third step of temperature rising reaction
Carrying out the second-stage temperature rise after the first-stage reaction is carried out for 60 minutes, raising the temperature of the sulfonation kettle to 120 ℃ in 15 minutes, and preserving the temperature for 60 minutes;
fourthly, post-treatment
After the reaction is finished, the catalyst is filtered and recovered, and the catalyst can be reused after being dried. Adding a large amount of water into the reacted materials, cooling to room temperature, adding 20% NaOH solution to adjust the pH, adjusting the adding speed to ensure that the temperature rise does not exceed 15 ℃, stopping adding alkali when the pH is 7.3, increasing the stirring speed, and quickly continuing stirring for 60 minutes.
And filtering, centrifugally dewatering, dissolving and decolorizing, crystallizing and purifying, drying and the like the materials after the neutralization reaction to prepare the sodium dimethyl isophthalate-5-sulfonate.
The quality indexes of the prepared product are shown in the table 3:
example 4 catalyst for synthesis of dimethyl isophthalate-5-sodium sulfonate and use thereof
Catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate
The catalyst comprises a composite carrier and an active component; the mass ratio of the active component to the composite carrier is 8: 100;
the composite carrier comprises a diatomite carrier and a rho-alumina carrier, wherein the mass ratio of the diatomite carrier to the rho-alumina carrier is 1: 2.5;
the active component comprises dibutyltin oxide and copper chloride, and the mass ratio of the dibutyltin oxide to the copper chloride is 1: 1;
the preparation method of the catalyst comprises the following steps:
(1) preparation of composite Carrier
And mixing and stirring the diatomite carrier and the rho-alumina carrier according to the mass ratio of 1:2.5 to obtain the composite carrier.
The preparation method of the diatomite carrier comprises the following steps: fully washing the diatomite with ultrapure water, drying in the air, putting the diatomite in a muffle furnace, firing for 4 hours at 650 ℃, and then activating for 2 hours at 100 ℃ to obtain a diatomite carrier after activation;
(2) active ingredient loading
A. Ball mill
Mixing dibutyltin oxide and copper chloride powder in proportion, adding the mixture into a ball mill, adding a composite carrier, mixing and grinding at the rotating speed of 500r/min for 6 hours to obtain a mixture of an active component and the composite carrier;
B. granulating
Adding a mixture of the active component and the composite carrier into a granulator, adding 5% of epoxy adhesive for granulation treatment, wherein the granularity of the mixed fine materials is less than or equal to 200 meshes, and obtaining catalyst prefabricated particles;
C. calcination of
And finally, calcining the catalyst preformed particles at the temperature of 280 ℃ for 4 hours to obtain the catalyst with the composite carrier.
Secondly, application of the catalyst in synthesis of dimethyl isophthalate-5-sulfonic acid
Charging
Putting fuming sulfuric acid into a sulfonation kettle, starting stirring, dropwise adding dimethyl isophthalate into the sulfonation kettle, and adding a catalyst, wherein the weight ratio of dimethyl isophthalate: 65% oleum = 1.363: 1, catalyst: dimethyl isophthalate =35: 100;
② first stage heating reaction
The temperature of the sulfonation kettle is raised from normal temperature to 100 ℃ within 20 minutes, and the reaction is carried out for 60 minutes;
third step of temperature rising reaction
Carrying out the second-stage temperature rise after the first-stage reaction is carried out for 60 minutes, raising the temperature of the sulfonation kettle to 120 ℃ in 10 minutes, and preserving the heat for 50 minutes at the temperature;
fourthly, post-treatment
After the reaction is finished, the catalyst is filtered and recovered, and the catalyst can be reused after being dried. Adding a large amount of water into the reacted materials, cooling to room temperature, adding 20% NaOH solution to adjust the pH, adjusting the adding speed to ensure that the temperature rise does not exceed 15 ℃, stopping adding alkali when the pH is 7.5, increasing the stirring speed, and quickly continuing stirring for 60 minutes.
And filtering, centrifugally dewatering, dissolving and decolorizing, crystallizing and purifying, drying and the like the materials after the neutralization reaction to prepare the sodium dimethyl isophthalate-5-sulfonate.
The quality indexes of the prepared product are shown in table 4:
finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A catalyst for synthesizing dimethyl isophthalate-5-sodium sulfonate is characterized by comprising a composite carrier and an active component;
the composite carrier comprises a diatomite carrier and a rho-alumina carrier, wherein the mass ratio of the diatomite carrier to the rho-alumina carrier is 1: 1.8-2.3;
the active component comprises dibutyltin oxide and copper chloride, and the mass ratio of the dibutyltin oxide to the copper chloride is 1: 0.7 to 1;
the mass ratio of the active component to the composite carrier of the catalyst is 5-10: 100, respectively;
the specific surface area of the supported catalyst is 700-1000 m2/g。
2. The catalyst for synthesizing sodium dimethyl isophthalate-5-sulfonate according to claim 1, wherein the preparation method of the catalyst comprises the steps of preparing a composite carrier and loading an active component;
the active component loading comprises calcination and is characterized in that the calcination temperature is 200-280 ℃, and the calcination time is 4-6 h.
3. The catalyst as claimed in claim 2, wherein the preparation of the composite carrier comprises the preparation of diatomite carrier, the diatomite carrier is fully washed with ultrapure water, dried, placed in a muffle furnace, burned at 650 ℃ for 4h, and then cooled to 100 ℃ for activation for 2 h.
4. The catalyst as claimed in claim 2, wherein the active component is loaded by ball milling at a ball mill rotation speed of 400-500r/min for 5-7 hours.
5. The catalyst for synthesizing the sodium dimethyl isophthalate-5-sulfonate as recited in claim 2, wherein the active component is loaded, the active component comprises granulation, the addition amount of the epoxy adhesive in the granulation accounts for 2-5% of the weight of the catalyst, and the particle size of the epoxy adhesive is less than or equal to 200 meshes.
6. The catalyst for synthesizing sodium dimethyl isophthalate-5-sulfonate as recited in claim 1, wherein the application of said catalyst comprises charging, first-stage heating reaction, second-stage heating reaction and post-treatment.
7. The catalyst for synthesizing sodium dimethyl isophthalate-5-sulfonate as recited in claim 6, wherein the weight ratio of the fed dimethyl isophthalate to 65% fuming sulfuric acid is 1.320-1.356: 1; the adding amount of the catalyst is 20-35% of dimethyl isophthalate by weight.
8. The catalyst for synthesizing sodium dimethyl isophthalate-5-sulfonate according to claim 6, wherein the first-stage heating reaction is carried out by heating the temperature of the sulfonation kettle from normal temperature to 90-100 ℃ within 20-30 minutes, and reacting for 60 minutes;
and (3) heating the sulfonation kettle to 115-120 ℃ in 10-15 minutes, and keeping the temperature for 50-80 minutes.
9. The catalyst for synthesizing sodium dimethyl isophthalate-5-sulfonate according to claim 6, wherein said post-treatment comprises filtration, cake drying and recovery; and adding 20% NaOH solution into the filtrate to adjust the pH value to 6.5-7.5, keeping the temperature rise to be not more than 15 ℃, dropwise adding to increase the stirring speed, and quickly continuing to stir for 60-65 minutes.
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| CN107759568A (en) * | 2016-08-22 | 2018-03-06 | 四川海思科制药有限公司 | Wo Nuolazan salt, crystal formation and its production and use |
| CN109336791A (en) * | 2018-11-16 | 2019-02-15 | 泰山医学院 | A kind of three monomer process Waste water concentrating material production M-phthalic acid binaryglycol ester -5- sodium sulfonate method |
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| CN107759568A (en) * | 2016-08-22 | 2018-03-06 | 四川海思科制药有限公司 | Wo Nuolazan salt, crystal formation and its production and use |
| CN109336791A (en) * | 2018-11-16 | 2019-02-15 | 泰山医学院 | A kind of three monomer process Waste water concentrating material production M-phthalic acid binaryglycol ester -5- sodium sulfonate method |
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