CN112961066A - Process for preparing terephthalamide from terephthalic acid - Google Patents
Process for preparing terephthalamide from terephthalic acid Download PDFInfo
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- CN112961066A CN112961066A CN202110189793.6A CN202110189793A CN112961066A CN 112961066 A CN112961066 A CN 112961066A CN 202110189793 A CN202110189793 A CN 202110189793A CN 112961066 A CN112961066 A CN 112961066A
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- reaction
- terephthalic acid
- ammonia gas
- terephthalamide
- esterification
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 126
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 103
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 82
- 238000005886 esterification reaction Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000005915 ammonolysis reaction Methods 0.000 claims abstract description 36
- 230000032050 esterification Effects 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000012065 filter cake Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 44
- 230000008569 process Effects 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 230000035484 reaction time Effects 0.000 claims description 15
- 239000000706 filtrate Substances 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 229910021529 ammonia Inorganic materials 0.000 description 17
- 239000007789 gas Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000006872 improvement Effects 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 description 4
- 229920002601 oligoester Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- -1 terephthalic acid diester Chemical class 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- XRBXGZZMKCBTFP-UHFFFAOYSA-N 4-(2,2-dihydroxyethoxycarbonyl)benzoic acid Chemical compound OC(O)COC(=O)C1=CC=C(C(O)=O)C=C1 XRBXGZZMKCBTFP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 238000007098 aminolysis reaction Methods 0.000 description 3
- 238000005660 chlorination reaction Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- ADYMLBFRZQQBMQ-UHFFFAOYSA-N 4-(hydroxyiminomethyl)benzaldehyde Chemical compound ON=CC1=CC=C(C=O)C=C1 ADYMLBFRZQQBMQ-UHFFFAOYSA-N 0.000 description 1
- BCBHDSLDGBIFIX-UHFFFAOYSA-N 4-[(2-hydroxyethoxy)carbonyl]benzoic acid Chemical compound OCCOC(=O)C1=CC=C(C(O)=O)C=C1 BCBHDSLDGBIFIX-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000011938 amidation process Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940064734 aminobenzoate Drugs 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing terephthalamide from terephthalic acid, which comprises the following steps: carrying out esterification reaction on terephthalic acid and alcohol, and discharging byproduct water generated by the reaction out of a reaction system; introducing ammonia gas into the obtained esterification solution to be subjected to ammonolysis to perform ammonolysis reaction to obtain a reaction vessel (marked as a reaction vessel I) filled with ammonolysis solution containing high-concentration ammonia gas; the reaction vessel I is connected with a reaction vessel (marked as a reaction vessel II) filled with the next batch of esterification liquid to be aminolyzed, so that the recovery of excessive ammonia gas is realized; and (3) cooling the ammonolysis solution containing low-concentration ammonia gas in the reaction vessel I, filtering, washing and drying a filter cake to obtain the terephthalamide. The invention adopts the route of esterification and ammonolysis of terephthalic acid to produce the terephthalamide, and the main byproduct in the reaction process is water, thereby conforming to the green production concept.
Description
Technical Field
The invention relates to the field of petrochemical industry, in particular to a method for preparing terephthalamide from terephthalic acid.
Background
Terephthalic acid is used as a raw material in the existing synthetic route, and is subjected to an acyl chlorination reaction to prepare terephthaloyl chloride, wherein common acyl chlorination reagents comprise thionyl chloride, phosphorus trichloride, phosphorus pentachloride, phosgene and the like; the terephthaloyl chloride reacts with ammonia sources such as ammonia gas and the like to obtain the terephthalamide. The method has mild reaction conditions, simple operation and higher product yield, but generates a large amount of chlorine-containing byproducts in the processes of acyl chlorination and ammoniation, has poor environmental benefit and does not conform to the green production concept.
In view of the above disadvantages, patent CN105016939 discloses a method for producing terephthalamide, which comprises adding a proper amount of terephthalic acid into a reaction kettle, charging ammonia gas (with a water content of 0.5 wt%) with a molar number 2.6 times that of terephthalic acid, or adding ammonium bicarbonate powder with an ammonium ion molar number 2.8 times that of terephthalic acid, sealing the reaction kettle, and carrying out a reaction at 305-320 ℃ for 0.5h under a stirring condition to obtain terephthalamide. The method can effectively reduce the discharge of three wastes, but has high reaction temperature and large reaction energy consumption; high reaction pressure, high requirement on equipment and the like. In patent CN104592040, terephthalic acid is used as a raw material, and is subjected to methyl esterification and ammoniation to synthesize terephthalamide, the reaction conditions are mild, the product yield is high, but two solvents such as methanol and water are required to be used in the reaction process, the operation is complex, and the continuous production is not facilitated; the acidic catalyst used in the esterification process and the alkaline water used in the washing process lead to an increase in the amount of wastewater discharged. Monoyuhua and the like (proceedings of the national institute of petrochemical engineering, Jiangsu, 2002,14(4):1-3) report a process for synthesizing terephthalamide by methyl esterification and amide taking terephthalic acid as a raw material, wherein the process is mild, but sulfuric acid is used as a catalyst in the methyl esterification process, so that the discharge amount of wastewater is increased; the esterification process is carried out in methanol, the amidation process is carried out in ethylene glycol, and different systems are adopted in the two-step reaction, so that the production procedures are increased.
In addition, a process for synthesizing terephthalamide from terephthalonitrile, p-xylylenediamine, terephthalaldehyde, and terephthalaldehyde oxime has been reported. Guo et al (Chemical Science,2019,10(45):10647-10652) reported a process for preparing terephthalamide by hydrolysis using terephthalonitrile as a raw material and ruthenium complex as a catalyst, which has clean process and mild conditions, but has limited source of terephthalonitrile and high cost due to the use of a noble metal catalyst. Joshi et al (Green Chemistry,2019,21(5):962-967) reported a process for preparing terephthalamide by oxygen oxidation using p-xylylenediamine as raw material and tetrabutylammonium hydroxide as catalyst, which has mild conditions and clean process, but the tetrabutylammonium hydroxide of p-xylylenediamine has high price and high cost. Park et al (Chemical Communications,2003, (15): 1936-. Shie et al (Journal of Organic Chemistry,2003,68(3):1158-1160) reported that terephthalaldehyde reacts with iodine in ammonia water at room temperature to obtain a terephthalonitrile intermediate, and then reacts with excessive 30% hydrogen peroxide to generate terephthalamide.
Accordingly, the present state of the art still requires a process for preparing terephthalamide from terephthalic acid, which is simple in reaction process and post-treatment, and does not require a catalyst, in order to overcome the aforementioned problems of the prior art processes.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing terephthalamide from terephthalic acid, which is suitable for industrial production.
In order to solve the above technical problems, the present invention provides a method for preparing terephthalamide from terephthalic acid, comprising the steps of:
1) and terephthalic acid and alcohol are mixed according to a ratio of 1: placing a reaction system formed by mixing 10-30 mol ratio in a reaction container, carrying out esterification reaction at esterification reaction temperature of 120-160 ℃ and normal pressure for 6-12 h, and introducing inert gas (such as nitrogen) or air into the reaction system in the esterification reaction process so as to lead the byproduct water generated by the reaction to carry and discharge the system (organic matter reflux reaction system such as alcohol);
after the esterification reaction is finished, cooling to room temperature to obtain an esterified liquid to be aminolyzed;
the reaction container is respectively provided with an air inlet valve and an air outlet valve;
2) introducing ammonia gas into the esterification solution to be subjected to ammonolysis, and carrying out ammonolysis reaction at the temperature of 60-90 ℃ and under the pressure of 0.5-1.5 MPa for 6-10 h;
the mol ratio of the ammonia gas to the terephthalic acid in the step 1) is 2.5-4.5: 1;
3) after the ammonolysis reaction in the step 2) is finished, obtaining a reaction vessel filled with ammonolysis liquid containing high-concentration ammonia gas, and marking as a reaction vessel I;
marking the reaction vessel (obtained in the step 1) filled with the next batch of esterification liquid to be aminolyzed as a reaction vessel II;
connecting an air outlet valve of the reaction container I with an air inlet valve of the reaction container II, opening the air outlet valve of the reaction container I and the air inlet valve of the reaction container II, heating the reaction container I to 140-160 ℃, keeping the temperature of the esterification liquid in the reaction container II at room temperature, setting the ammonia gas recovery time to be 0.5-1 h, and closing the air outlet valve of the reaction container I and the air inlet valve of the reaction container II after the ammonia gas recovery time is up;
description of the drawings: in general, the reaction vessel I and the reaction vessel II adopt the same size and specification; different specifications can be selected, but ammonia gas is required to be recovered to the maximum extent, and the larger the reaction vessel II is, the more the esterification liquid is, the higher the ammonia gas recovery rate is;
in this step 3): after the ammonolysis reaction in the step 2) is finished, recovering excessive ammonia gas; namely, the step 3) is an excessive ammonia recovery process, and the reaction vessel I is heated to 140-160 ℃ to reduce the solubility of ammonia and improve the ammonia recovery rate.
4) And cooling the ammonolysis solution containing low-concentration ammonia gas in the reaction container I obtained in the step 3) (cooling to room temperature), filtering, washing and drying a filter cake to obtain the terephthalamide.
As an improvement of the process for producing terephthalamide from terephthalic acid of the present invention:
in step 3): and (3) after the ammonia gas recovery time is up, supplementing ammonia gas into the reaction vessel II until the total amount of ammonia gas in the reaction vessel II (ammonia gas supplied by the reaction vessel I and supplemented ammonia gas) meets the molar ratio of the ammonia gas to the terephthalic acid set in the step 2).
As a further improvement of the process for producing terephthalamide from terephthalic acid of the present invention:
and in the step 4), the filtrate obtained by filtering is recycled and reused.
The filtrate is mainly alcohol, and also comprises a small amount of by-product oligoester and a trace amount of terephthalic acid; the filtrate can be directly recycled and reused as raw materials and solvents for the esterification reaction of subsequent batches.
As a further improvement of the process for producing terephthalamide from terephthalic acid of the present invention:
in the step 1), the alcohol is ethylene glycol, 1, 3-propylene glycol or 2, 3-butanediol.
As a further improvement of the process for producing terephthalamide from terephthalic acid of the present invention:
the volume ratio of the flow rate of the inert gas/air per minute to the alcohol is 0.3-0.5: 1.
as a further improvement of the process for producing terephthalamide from terephthalic acid of the present invention:
in the step 4), the filter cake is washed by methanol.
As a further improvement of the process for producing terephthalamide from terephthalic acid of the present invention:
in the step 1):
the molar ratio of terephthalic acid to alcohol is 1: 15-30 ℃, wherein the esterification reaction temperature is 130-150 ℃, and the esterification reaction time is 8-10 h; the volume ratio of the flow rate of the inert gas/air per minute to the alcohol is 0.35-0.45: 1;
in the step 2):
the mol ratio of ammonia gas to terephthalic acid in the step 1) is 3-4: 1, the ammonolysis reaction temperature is 70-80 ℃, and the ammonolysis reaction time is 7-9 h.
In the invention, firstly, a certain amount of terephthalic acid and alcohol are mixed and stirred to prepare slurry, then esterification reaction is carried out under normal pressure and heating condition to generate terephthalic acid diester and oligoester, and byproduct water is brought out by inert gas or air, and the method specifically comprises the following steps: the gas is introduced from the bottom of the reactor, flows through the reaction liquid (reaction system) in a bubbling mode, and finally escapes from the top of the reactor, and meanwhile, the by-product water and a small amount of alcohol are carried away. The reaction progress was monitored by HPLC. The conversion rate of terephthalic acid in the esterification reaction is at least 99.0 percent and can reach 99.5 percent at most.
After the esterification is finished, the esterification solution is directly subjected to ammonolysis reaction, and the reaction process is monitored by HPLC. The conversion rate of the diester terephthalate and the oligoester in the ammonolysis reaction is at least 98.0 percent and can reach 99.0 percent at most.
Compared with the prior art, the invention has the following technical advantages:
1) the terephthalic acid is used for producing the terephthalamide through a route of esterification and ammonolysis, and the main byproduct in the reaction process is water, so that the method conforms to the green production concept;
2) the unique action of alcohol in esterification and aminolysis reaction of terephthalic acid diester is utilized, and a gas stripping process is adopted to discharge water which is a byproduct generated in the esterification reaction, so that a catalyst is not needed in the reaction process;
3) the esterification and ammonolysis one-pot reaction process is adopted, and the ammonification reaction can be carried out without separating and purifying the reaction liquid after the esterification reaction is finished, so that the production process is simplified, and the method is suitable for industrial production;
4) the reaction conditions are mild, and the requirements on equipment are low.
5) The reaction process and the post-treatment are simple.
Detailed Description
The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.
The detection method comprises the following steps: the conversion rate of raw materials and the purity of products are determined by a conventional High Performance Liquid Chromatography (HPLC), and the recovery rate of ammonia and the yield of products are determined by a conventional weighing method.
The room temperature is generally 5 to 30 ℃.
Example 1, a process for the preparation of terephthalamide from terephthalic acid:
1) adding 1mol of terephthalic acid and 22.5mol of ethylene glycol (about 1250mL) into a slurry tank, mixing and stirring to obtain slurry;
selecting a reactor provided with a stirring device, a temperature measuring device and a rectifying device, injecting slurry into the reactor through a sample injection pump, carrying out esterification reaction under the conditions of normal pressure and 140 ℃, continuously introducing air from the bottom of the reactor at the flow rate of 500mL/min, wherein the volume ratio of the flow rate per minute of the ethylene glycol to the flow rate per minute of the air is 1: 0.4; the top temperature of the rectifying device is 110-120 ℃; so that the air flow and the carried by-product water are brought out of the system, and the ethylene glycol flows back to the system; when the reaction time is 9 hours by HPLC monitoring, the conversion rate of the terephthalic acid reaches 99.5 percent, and the reaction is stopped; cooling to room temperature (about 30 ℃) to obtain esterified liquid to be ammonolyzed;
2) introducing 3.5mol of ammonia gas into the esterification solution to be aminolyzed, carrying out aminolysis reaction under the conditions of 0.8MPa and 75 ℃ after the ammonia gas is introduced, and stopping the reaction when the HPLC monitoring reaction time is 8h and the conversion rate of the dihydroxyethyl terephthalate and the oligoester reaches 99.0 percent to obtain the aminolysis solution containing high-concentration ammonia gas;
3) connecting a gas outlet valve of a reactor (marked as a reactor I) filled with ammonolysis solution containing high-concentration ammonia with a gas inlet valve of a reactor (marked as a reactor II) filled with next batch of esterification liquid to be ammonolyzed, opening a gas outlet valve of the reactor I and a gas inlet valve of the reactor II, heating the reactor I to 150 ℃, keeping the temperature of the esterification liquid in the reactor II not higher than 30 ℃, closing the gas outlet valve of the reactor I and the gas inlet valve of the reactor II after 1h, obtaining ammonolysis solution containing low-concentration ammonia in the reactor I, wherein the recovery rate of the ammonia is 72.5 percent, and the actual consumption of the ammonia is 120.6 percent of the theoretical amount;
the ammonia recovery rate α and the actual ammonia consumption amount β are calculated by the following formulas:
in the formula: w0-recovering the mass of the pre-reactor II, g;
W1-the mass of the recovered vessel II, g;
W2-the amount of ammonia gas, g, required by the ammonolysis reaction theory;
W3-ammonia charge, g, of the ammonolysis reaction.
4) Cooling the ammonolysis solution containing low-concentration ammonia gas to room temperature, filtering to obtain filtrate and filter cakes respectively, washing the filter cakes twice by using methanol (100 ml of methanol is adopted for each washing), and drying (drying under reduced pressure at 80 ℃ to constant weight) to obtain the product of the terephthalamide, wherein the yield is 95.0%, and the purity is 99.0%.
The filtrate mainly contains glycol (the content is about 97.0 percent), and also contains a very small amount of dihydroxy ethyl terephthalate, terephthalamide, monohydroxyethyl terephthalate, hydroxy ethyl p-aminobenzoate and a trace amount of terephthalic acid; the filtrate can be directly recycled and reused as raw materials and solvents for subsequent esterification reaction.
In examples 2 to 5, the amount of terephthalic acid was kept constant, the molar ratio of terephthalic acid to ethylene glycol was changed, the volume ratio of ethylene glycol to air flow per minute was kept constant, the other operations were the same as in example 1, examples 2 to 5 were obtained, and the process parameters and the reaction results are shown in table 1.
TABLE 1
| Examples | Molar ratio of terephthalic acid to ethylene glycol | Product yield (%) | Product purity (%) |
| 2 | 1：15 | 94.5 | 98.0 |
| 3 | 1：20 | 94.8 | 98.6 |
| 4 | 1：25 | 95.2 | 99.1 |
| 5 | 1：30 | 95.5 | 99.5 |
In examples 6 to 9, the esterification reaction temperature was changed, and the other operations were the same as in example 1 to obtain examples 6 to 9, and the process parameters and the reaction results are shown in table 2.
TABLE 2
Example 10 was carried out in the same manner as in example 1 except that the kind of gas was changed to obtain example 10, and the process parameters and the reaction results were shown in Table 3.
TABLE 3
| Examples | Kind of inert gas | Product yield (%) | Product purity (%) |
| 10 | Nitrogen gas | 95.1 | 99.1 |
Examples 11 to 14 were obtained by changing the flow rate of air and performing the same operation as in example 1, except that the process parameters and the reaction results were as shown in Table 4.
TABLE 4
| Examples | Air flow (mL/min) | Product yield (%) | Product purity (%) |
| 11 | 375 | 94.0 | 98.0 |
| 12 | 437.5 | 94.7 | 98.5 |
| 13 | 562.5 | 95.2 | 99.2 |
| 14 | 625 | 95.3 | 99.3 |
In examples 15 to 18, the esterification reaction time was changed, and the other operations were the same as in example 1 to obtain examples 15 to 18, and the process parameters and the reaction results are shown in table 5.
TABLE 5
| Examples | Esterification reaction time (h) | Product yield (%) | Product purity (%) |
| 15 | 6 | 93.0 | 97.5 |
| 16 | 8 | 94.5 | 98.5 |
| 17 | 10 | 95.4 | 99.1 |
| 18 | 12 | 95.7 | 99.3 |
Examples 19 to 20 were prepared by changing the alcohol type and keeping the amounts of terephthalic acid and alcohol unchanged, and the other operations were the same as in example 1, to obtain examples 19 to 20, and see Table 6 for the process parameters and reaction results.
TABLE 6
| Examples | Alcohol(s) | Product yield (%) | Product purity (%) |
| 19 | 1, 3-propanediol | 94.2 | 98.3 |
| 20 | 2, 3-butanediol | 93.0 | 97.5 |
Examples 21 to 24 were prepared by changing the molar ratio of terephthalic acid to ammonia gas while keeping the amount of terephthalic acid unchanged, and the other operations were the same as in example 1, to obtain examples 21 to 24, and the process parameters and reaction results are shown in Table 7.
TABLE 7
| Examples | Molar ratio of terephthalic acid to ammonia | System pressure (MPa) | Product yield (%) | Product purity (%) |
| 21 | 1：2.5 | 0.5 | 94.0 | 98.0 |
| 22 | 1：3 | 0.6 | 94.7 | 98.5 |
| 23 | 1：4 | 1.1 | 95.5 | 99.3 |
| 24 | 1：4.5 | 1.5 | 96.0 | 99.5 |
In examples 25 to 28, the ammonolysis reaction temperature and pressure were varied, and the other operations were the same as in example 1, to obtain examples 25 to 28, and the process parameters and reaction results are shown in Table 8.
TABLE 8
| Examples | Ammonolysis reaction temperature (. degree.C.) | System pressure (MPa) | Product yield (%) | Product purity (%) |
| 25 | 60 | 0.5 | 94.0 | 98.0 |
| 26 | 70 | 0.6 | 94.7 | 98.5 |
| 27 | 80 | 1.1 | 95.2 | 99.2 |
| 28 | 90 | 1.5 | 95.3 | 99.3 |
In examples 29 to 32, the ammonolysis reaction time was changed, and the other operations were the same as in example 1, to obtain examples 29 to 32, and the process parameters and the reaction results are shown in Table 9.
TABLE 9
| Examples | Ammonolysis reaction time (h) | Product yield (%) | Product purity (%) |
| 29 | 6 | 93.6 | 98.0 |
| 30 | 7 | 94.4 | 98.5 |
| 31 | 9 | 95.2 | 99.2 |
| 32 | 10 | 95.3 | 99.3 |
Example 33 Recycling and use
The first recovery and reuse: the filtrate obtained in example 1 was used in place of ethylene glycol as a starting material, and the amount by volume was kept constant, and the rest was the same as in example 1.
When the esterification reaction time is 9 hours, the conversion rate of the terephthalic acid is 99.5 percent, the yield of the terephthalamide is 95.0 percent, and the purity is 99.0 percent.
The above recovery and reuse are repeated, and when the fifth time, the conversion rate of the terephthalic acid is 99.0 percent, the yield of the terephthalamide is 94.0 percent, and the purity is 97.5 percent. At this time, the filtrate contains more impurities, the product purity is reduced, and the filtrate needs to be purified and then recycled. The purification specifically comprises the following steps: and (4) carrying out reduced pressure distillation on the filtrate obtained after the fifth reaction at the temperature of 120-160 ℃ to obtain the ethylene glycol with the purity of about 99.0%.
Example 34, next batch:
and (3) after the ammonia gas recovery time is up, supplementing ammonia gas into the reaction vessel II until the total amount of ammonia gas in the reaction vessel II (ammonia gas supplied by the reaction vessel I and supplemented ammonia gas) meets the molar ratio of the ammonia gas to the terephthalic acid set in the step 2), and the balance is equal to that in the example 1.
The results obtained were: when the ammonolysis reaction time is 8 hours, the conversion rate of the dihydroxyethyl terephthalate and the oligomeric ester reaches 99.0 percent, the yield of the terephthalamide is 95.0 percent, and the purity is 99.0 percent;
in practice, the results obtained remain substantially unchanged after repeating the above five batches.
Comparative examples 1,
Inert gas or air is not introduced in the esterification reaction process, other operations are identical to those of the example 1, and the comparative example 1 is obtained;
when the reaction is carried out for 9 hours, the conversion rate of the terephthalic acid is only 80.3 percent;
after 16h of reaction, the conversion rate of terephthalic acid reaches 98.0%, the yield of the terephthalamide is 93.5%, and the purity of the terephthalamide is 96.1%.
Comparative examples 2,
Ammonia gas is not recovered in the ammonolysis reaction process, other operations are equal to those of the embodiment 1, and a comparative example 2 is obtained;
the ammonia consumption is 175.0 percent of the theoretical amount and is increased by 45.0 percent for every 1kg of terephthalamide produced.
The increase γ in ammonia gas consumption was calculated by the following formula:
γ＝(β′-β)×100％
in the formula: β' — consumption of ammonia without recovery of ammonia, g;
beta-consumption of ammonia gas, g, when ammonia gas is recovered.
Comparative example 3, the amount of ethylene glycol used in example 1 was changed to 8mol, that is, terephthalic acid: ethylene glycol 1: 8, the remainder being equivalent to example 1.
The results obtained were: when the esterification reaction time is 9 hours, the conversion rate of the terephthalic acid reaches 95.0 percent, the yield of the terephthalamide is 92.2 percent, and the purity is 91.7 percent.
Comparative example 4, the ethylene glycol in example 1 was changed to methanol, the molar amount was kept unchanged, the esterification temperature was changed to 50 ℃, and the rest was the same as in example 1.
The results obtained were: when the esterification reaction time is 9 hours, the conversion rate of the terephthalic acid reaches 90.8 percent, the yield of the terephthalamide is 86.6 percent, and the purity is 81.0 percent.
Comparative example 5, the amount of ammonia used in example 1 was changed to 2mol, that is, terephthalic acid: ammonia gas 1: 2, the remainder being equivalent to example 1.
The results obtained were: when the ammonolysis reaction time is 8 hours, the conversion rate of the dihydroxyethyl terephthalate and the oligomeric ester reaches 90.3 percent, the yield of the terephthalamide is 85.4 percent, and the purity is 82.1 percent.
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (7)
1. A process for preparing terephthalamide from terephthalic acid, characterized by comprising the steps of:
1) and terephthalic acid and alcohol are mixed according to a ratio of 1: 10-30 mol ratio, placing the reaction system into a reaction container, carrying out esterification reaction at the esterification reaction temperature of 120-160 ℃ and under normal pressure for 6-12 h, and introducing inert gas or air into the reaction system in the esterification reaction process so as to discharge the byproduct water generated by the reaction out of the system;
after the esterification reaction is finished, cooling to room temperature to obtain an esterified liquid to be aminolyzed;
the reaction container is respectively provided with an air inlet valve and an air outlet valve;
2) introducing ammonia gas into the esterification solution to be subjected to ammonolysis, and carrying out ammonolysis reaction at the temperature of 60-90 ℃ and under the pressure of 0.5-1.5 MPa for 6-10 h;
the mol ratio of the ammonia gas to the terephthalic acid in the step 1) is 2.5-4.5: 1;
3) after the ammonolysis reaction in the step 2) is finished, obtaining a reaction vessel filled with ammonolysis liquid containing high-concentration ammonia gas, and marking as a reaction vessel I;
marking the reaction vessel filled with the next batch of esterification liquid to be aminolyzed as a reaction vessel II;
connecting an air outlet valve of the reaction container I with an air inlet valve of the reaction container II, opening the air outlet valve of the reaction container I and the air inlet valve of the reaction container II, heating the reaction container I to 140-160 ℃, keeping the temperature of the esterification liquid in the reaction container II at room temperature, setting the ammonia gas recovery time to be 0.5-1 h, and closing the air outlet valve of the reaction container I and the air inlet valve of the reaction container II after the ammonia gas recovery time is up;
4) and cooling the ammonolysis solution containing low-concentration ammonia gas in the reaction container I obtained in the step 3), filtering, washing and drying a filter cake to obtain the terephthalamide.
2. The process for producing terephthalamide from terephthalic acid according to claim 1, characterized in that:
in step 3): and (3) after the ammonia gas recovery time is up, supplementing ammonia gas into the reaction vessel II until the total amount of the ammonia gas in the reaction vessel II meets the molar ratio of the ammonia gas to the terephthalic acid set in the step 2).
3. The process for producing terephthalamide from terephthalic acid according to claim 1 or 2, characterized in that:
and in the step 4), the filtrate obtained by filtering is recycled and reused.
4. The process for producing terephthalamide from terephthalic acid according to any one of claims 1 to 3, wherein:
in the step 1), the alcohol is ethylene glycol, 1, 3-propylene glycol or 2, 3-butanediol.
5. The process of claim 4 for the preparation of terephthalamide from terephthalic acid, wherein:
the volume ratio of the flow rate of the inert gas/air per minute to the alcohol is 0.3-0.5: 1.
6. the process for producing terephthalamide from terephthalic acid according to claim 5, characterized in that:
in the step 4), the filter cake is washed by methanol.
7. The process for producing terephthalamide from terephthalic acid according to any one of claims 1 to 6, wherein:
in the step 1):
the molar ratio of terephthalic acid to alcohol is 1: 15-30 ℃, wherein the esterification reaction temperature is 130-150 ℃, and the esterification reaction time is 8-10 h; the volume ratio of the flow rate of the inert gas/air per minute to the alcohol is 0.35-0.45: 1;
in the step 2):
the mol ratio of ammonia gas to terephthalic acid in the step 1) is 3-4: 1, the ammonolysis reaction temperature is 70-80 ℃, and the ammonolysis reaction time is 7-9 h.
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