CN118179589A - Catalyst for synthesizing acrylic acid and preparation method and application thereof - Google Patents
Catalyst for synthesizing acrylic acid and preparation method and application thereof Download PDFInfo
- Publication number
- CN118179589A CN118179589A CN202211602171.2A CN202211602171A CN118179589A CN 118179589 A CN118179589 A CN 118179589A CN 202211602171 A CN202211602171 A CN 202211602171A CN 118179589 A CN118179589 A CN 118179589A
- Authority
- CN
- China
- Prior art keywords
- solvent
- reaction
- catalyst
- acrylic acid
- acetonitrile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title claims abstract description 41
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000002904 solvent Substances 0.000 claims abstract description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 20
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000005977 Ethylene Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 18
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 15
- 239000012153 distilled water Substances 0.000 claims abstract description 15
- 150000002357 guanidines Chemical class 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000005349 anion exchange Methods 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 239000005457 ice water Substances 0.000 claims abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 93
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 51
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- NISGSNTVMOOSJQ-UHFFFAOYSA-N cyclopentanamine Chemical compound NC1CCCC1 NISGSNTVMOOSJQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- 230000032798 delamination Effects 0.000 claims description 2
- 238000005342 ion exchange Methods 0.000 claims description 2
- 229940100684 pentylamine Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 description 19
- -1 Acrylic ester Chemical class 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 230000008602 contraction Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- CGWBIHLHAGNJCX-UHFFFAOYSA-N 2-butylguanidine Chemical compound CCCCNC(N)=N CGWBIHLHAGNJCX-UHFFFAOYSA-N 0.000 description 1
- AJGAPBXTFUSKNJ-UHFFFAOYSA-N 2-cyclohexylguanidine Chemical compound NC(=N)NC1CCCCC1 AJGAPBXTFUSKNJ-UHFFFAOYSA-N 0.000 description 1
- CTLOWYRNTUVMJF-UHFFFAOYSA-N 2-cyclopentylguanidine Chemical compound NC(N)=NC1CCCC1 CTLOWYRNTUVMJF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a catalyst for synthesizing acrylic acid and a preparation method thereof, comprising (1) dissolving tetramethyl urea in a solvent A, adding phosphorus oxychloride under the protection of nitrogen for reaction, then adding alkylamine for reaction, then adding distilled water for reaction, standing for layering, adding NaOH into a lower layer liquid, and distilling an upper layer liquid after layering to obtain distillate; (2) Dissolving the distillate into a solvent B, adding a mixed solution of methyl iodide and the solvent C under the protection of ice-water bath and nitrogen, continuing to react after the system is restored to room temperature, distilling at normal pressure, and washing to obtain I ‑ -ion organic guanidine salt; (3) Anion exchange is carried out on non-I ‑ ion metal salt and organic guanidine salt of I ‑, then dichloromethane is added, an oil layer is separated, and the catalyst is obtained through washing, drying and distillation. The catalyst provided by the invention is suitable for directly synthesizing acrylic acid by taking CO 2 and ethylene as raw materials, and has the advantages of low reaction temperature, high product yield and the like.
Description
Technical Field
The invention relates to synthesis of acrylic acid, in particular to a catalyst for synthesizing acrylic acid, a preparation method and application thereof.
Background
With the increasing reliance of modern society on petrochemical resources, the increasing problem of CO 2 emissions has been more than an environmental problem. The greenhouse effect caused by the rapid increase of CO 2 seriously threatens the survival of human beings. The global energy shortage and the increasingly serious environmental problems caused by CO 2 have forced people to find ways to solve these problems, and thus have focused on the disposal of CO 2. The most direct CO 2 treatment method is to consume CO 2 more, and realize the recycling of CO 2 so as to fundamentally solve the problem of CO 2. The chemical utilization of CO 2 is one of important means for realizing the recycling of CO 2, and particularly, the massive utilization of CO 2 in large-scale chemical production plays a role in reducing the emission of the CO 2.
Acrylic ester is an important organic synthesis intermediate and a monomer for synthesizing a polymer, and has wide application in industries such as coating, medicine, leather, papermaking, adhesives and the like. The main production method of the acrylic ester comprises the following steps: acrylonitrile hydrolysis, propylene oxidation, ketene, wherein the propylene oxidation accounts for a greater specific gravity of the total acrylate production capacity. With the continuous development of the chemical industry, the demand for acrylic ester is growing, so new catalytic systems and new synthetic routes are continuously sought to meet the requirements of areas with different raw material advantages, and the production capacity of acrylic ester is increased.
The method for synthesizing the acrylic acid or the acrylic ester by adopting the ethylene and the CO 2 obviously has more economic advantages and green chemical industry advantages. This route is currently considered to be atomically economical and the reaction conditions are very mild. Meanwhile, the method provides an economic and effective way for recycling and efficiently utilizing the greenhouse gas CO 2.
CN101745428a discloses a catalyst for catalytic conversion of carbon dioxide into methacrylic acid and application, which adopts cerium oxide supported polyoxometallate catalyst, uses carbon dioxide and propylene as raw materials, and catalyzes and synthesizes methacrylic acid directly. Wherein the cerium oxide supported polyoxometallate catalyst consists of polyoxometallate and cerium oxide. The catalyst has high activity, high selectivity to target products and stable catalytic performance. However, the application temperature of the catalyst is 300 ℃, and the reaction temperature is higher.
Cheng Qingyan et al report in volume 24, 7 th and pages 558-562 of the journal of catalytic theory that Ni 2(Et)2/SiO2 catalyzes carbon dioxide and propylene to directly synthesize methacrylic acid, ni 2(Et)2/SiO2 is used as a catalyst, carbon dioxide and propylene are used as raw materials to directly synthesize methacrylic acid in a fixed bed, and the propylene conversion rate is 1.58% under the conditions that the molar ratio of carbon dioxide to propylene is 2, the airspeed is 1500h -1, the reaction pressure is 0.5MPa and the reaction temperature is 120 ℃. It can be seen that the propylene conversion and methacrylic acid yield were low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a catalyst for synthesizing acrylic acid, a preparation method and application thereof. The catalyst provided by the invention is suitable for directly synthesizing acrylic acid by taking CO 2 and ethylene as raw materials, and has the advantages of low reaction temperature, high product yield and the like.
The preparation method of the catalyst for synthesizing acrylic acid provided by the invention comprises the following steps:
(1) Dissolving tetramethylurea in a solvent A, adding phosphorus oxychloride under the protection of nitrogen for reaction, then adding alkylamine for reaction, then adding water for continuous reaction, standing for layering after the reaction, adding NaOH into a lower layer solution, and distilling an upper layer solution after layering to obtain distillate;
(2) Dissolving distillate into a solvent B, adding a mixed solution of methyl iodide and the solvent C under the protection of ice-water bath and nitrogen, continuing to react after the system is restored to room temperature, distilling at normal pressure after the reaction, and washing residual liquid to obtain I - ion organic guanidine salt;
(3) Anion exchange is carried out on non-I - ion metal salt and organic guanidine salt of I -, then dichloromethane is added, an oil layer is separated, and the catalyst is obtained through washing, drying and distillation.
In the method of the present invention, the solvent a in the step (1) is at least one of acetonitrile, benzene, toluene, tetrahydrofuran, etc., preferably toluene. Further, it is preferable to remove water and oxygen from the solvent A, specifically, in the presence of sodium metal and benzophenone, reflux for 3 hours and then evaporate the solvent to further increase the reactivity of the catalyst.
In the method of the invention, the volume ratio of the solvent A to the tetramethylurea in the step (1) is 5-20:1, preferably 8-16:1.
In the method of the present invention, the molar ratio of the tetramethylurea to the phosphorus oxychloride in the step (1) is 0.5:1 to 1:5, preferably 0.5:1 to 1:3.
In the method of the invention, the phosphorus oxychloride is added in the step (1) under the protection of nitrogen, and the reaction time is 2-15 hours, preferably 4-14 hours.
In the process of the present invention, the alkylamine in step (1) is at least one of C4-C6 alkylamines, such as butylamine, pentylamine, hexylamine, cyclopentylamine or cyclohexylamine, and the like, preferably cyclopentylamine or cyclohexylamine.
In the method of the present invention, the molar ratio of the alkylamine to tetramethylurea in the step (1) is 1:0.5 to 1:3, preferably 1:0.7 to 1:2. After the addition of the alkylamine, the reaction time is 20 to 80 hours, preferably 25 to 60 hours.
In the method of the invention, the volume ratio of the distilled water to the solvent A added in the step (1) is 2.5:1-0.7:1, preferably 2:1-1:1; the reaction time is 2 to 15 hours, preferably 4 to 12 hours after the addition.
In the method of the invention, the standing delamination time in the step (1) is 5 to 60 minutes, preferably 10 to 40 minutes.
In the method of the invention, the molar ratio of NaOH to phosphorus oxychloride in the step (1) is 10:1-3:1, preferably 8:1-4:1.
In the method of the invention, the distillate at 128-132 ℃ is taken out from the upper layer liquid after layering in the step (1) under the condition of 30-32 mmHg.
In the method of the present invention, the solvent B in the step (2) is at least one of acetonitrile, benzene, toluene, tetrahydrofuran, and the like, and acetonitrile is preferred. The volume ratio of the solvent B to the distillate is 30:1-10:1, preferably 20:1-15:1.
In the method of the present invention, the solvent C in the step (2) is at least one of acetonitrile, benzene, toluene, tetrahydrofuran, etc., preferably benzene.
In the process of the present invention, the volume ratio of methyl iodide to solvent C in step (2) is 1:5 to 1:20, preferably 1:10 to 1:17. The volume ratio of the solvent B to the mixed solution of methyl iodide and the solvent C is 1-5:1, preferably 1.5-4:1. When the mixed solution of methyl iodide and the solvent C is added, the flow rate is controlled to be 0.5-10 mL/min, preferably 1-7 mL/min.
In the method, in the step (2), after the system is restored to the room temperature, the reaction is continued for 24-36h.
In the process of the present invention, the reaction in step (2) is followed by atmospheric distillation at 50-150 ℃.
In the method, ethyl acetate is adopted for washing the residual liquid in the step (2), the residual liquid is washed for 3 to 5 times, and the ethyl acetate is removed by vacuum suction filtration after the washing.
In the method of the present invention, the non-I - ion metal salt in step (3) is at least one metal salt selected from BF 4 -、PF6 -、CH3COO-、CH3CH(OH)COO- or N (CN) 2 -, preferably a metal salt having PF 6 - as an anion. The metal ion in the metal salt is at least one of Na +,Mg2+,Zn2+,Pb2+, ca 2+, and the like, and preferably Na + or Pb 2+.
In the method of the invention, the molar ratio of the organic guanidine salt of the I - ion to the metal salt of the non-I - ion in the step (3) is 1:1-1:3, preferably 1:1-1:2.
In the method, the ion exchange reaction in the step (3) is carried out for 0.5-5h at room temperature, and after the reaction is finished, dichloromethane is added, and then an oil layer is separated.
In the method, distilled water is adopted in the washing in the step (3), anhydrous sodium sulfate is adopted in the drying, and the solvent is distilled off at normal pressure to obtain the catalyst.
The catalyst for synthesizing acrylic acid is prepared by the method. The prepared catalyst mainly comprises 1.1.3.3-tetramethyl-2-alkyl guanidine salt of anion non-I -, wherein alkyl guanidine is at least one of butyl guanidine, cyclopentyl guanidine, cyclohexyl guanidine and the like, and the anion is at least one of BF 4 -、PF6 -、CH3COO-、CH3CH(OH)COO- or N (CN) 2 - and the like.
The invention also provides a method for synthesizing the acrylic acid, which takes CO 2 and ethylene as raw materials and acetonitrile as a solvent, and the catalyst prepared by the method of the invention is used for directly synthesizing the acrylic acid. Wherein the mol ratio of ethylene to carbon dioxide is 1:1-1:10, preferably 1:3-1:8; the reaction temperature is 50-150 ℃, preferably 70-130 ℃; the reaction pressure is 0.5 to 6.0MPa, preferably 1.0 to 5.5MPa.
In the synthesis method, the catalyst accounts for 5 to 7.5 percent of the total amount of the reaction system.
In the synthesis method, the ratio of the catalyst to the acetonitrile addition amount is 2-4.5 g:100-200 mL.
Compared with the prior art, the invention has the following advantages:
(1) The invention prepares the organic guanidine salt with the anion of I - ion, and then carries out anion exchange with the metal salt with the anion of non-I - ion, thereby preparing the organic guanidine salt with the anion of non-I - ion, and realizing the synthesis of the catalyst.
(2) The catalyst prepared by the invention is used in the reaction process of directly synthesizing acrylic acid from ethylene and CO 2, can obtain high-yield acrylic acid, and the synthesis temperature is obviously reduced.
(3) In the presence of the catalyst, acetonitrile is used as a solvent in the process of synthesizing acrylic acid from ethylene and CO 2, so that the catalyst has good CO 2 solubility, is favorable for activating CO 2 by the catalyst, and promotes the reaction.
Drawings
FIG. 1 is an infrared spectrum of the catalyst prepared in example 1 of the present invention.
Detailed Description
The catalyst of the invention, its preparation and use are described in further detail below in connection with the specific examples. The embodiments and specific operation procedures are given on the premise of the technical scheme of the invention, but the protection scope of the invention is not limited to the following embodiments.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores. In the invention, the percentage content is weight percentage content.
In the embodiment of the invention, acrylic acid is analyzed by adopting an Agilent GC-7820A type gas chromatograph, a chromatographic column is a 30m multiplied by 530 mu m multiplied by 1 mu m capillary column, temperature programming is adopted, the temperature is kept at 230 ℃ for 10 minutes, and the temperature of a detector is: 250 ℃; quantitative analysis was performed using a normalization method. The structure of the prepared 1.1.3.3-tetramethyl-2-alkylguanidine salt of anionic non-I - was characterized by infrared spectroscopy.
Example 1
(1) Firstly, dissolving tetramethyl urea in toluene, wherein the volume ratio of toluene to tetramethyl urea is 9:1, adding phosphorus oxychloride under the protection of nitrogen, reacting for 8 hours at room temperature, adding cyclohexylamine, reacting for 25 hours at room temperature, adding distilled water, the volume ratio of distilled water to toluene is 2:1, continuing to react for 8 hours, and standing for layering for 30 minutes. NaOH is added into the lower layer liquid, and the mol ratio of NaOH to phosphorus oxychloride is 5:1. Drying the upper layer liquid after layering, distilling, and collecting distillate at 128-132 deg.C under 32 mmHg;
(2) The distillate is taken and dissolved in acetonitrile, the volume ratio of the distillate to the acetonitrile is 1:16, the mixed solution of methyl iodide and benzene is added under the cooling of ice water bath and the protection of nitrogen, wherein the volume ratio of methyl iodide to benzene is 1:12, the volume ratio of the mixed solution of acetonitrile and methyl iodide to benzene is 2:1, and the flow rate is controlled to be 5mL/min. After the system is restored to room temperature, stirring and reacting for 24 hours, distilling at normal pressure after the reaction is finished, evaporating the solvent, and washing residual liquid with ethyl acetate for three times. Removing ethyl acetate by vacuum suction filtration after washing to obtain 1.1.3.3-tetramethyl-2-cyclohexylguanidine salt of I -;
(3) The sodium salt with anions of PF 6 - and 1.1.3.3-tetramethyl-2-cyclohexylguanidine salt with anions of I - are subjected to anion exchange, the molar ratio of the organic guanidine salt with anions of I - to the non-I - metal salt is 1:1, the reaction is carried out for 3 hours at room temperature, methylene dichloride is added after the reaction to separate an oil layer, then distilled water is used for washing, anhydrous sodium sulfate is used for drying, the anhydrous sodium sulfate is removed by suction filtration, and the solvent is removed by normal pressure distillation, so that the catalyst is obtained.
As can be seen from fig. 1, in the prepared catalyst, a telescopic vibration absorption peak of c=n is found at 1596cm -1; the 2933cm -1 and 2862cm < -1 > are the telescopic vibration absorption peaks of C-H bonds in methyl and methylene; 1476cm -1,1457cm-1 and 1411cm -1 are the flexural vibration absorption peaks of the C-H bonds in methyl and methylene; C-N (C-N bond expansion and contraction vibration absorption peak in CH 3)2 structure; C-N bond expansion and contraction vibration absorption peak in CH 2)2 - structure; and P-F expansion and contraction vibration absorption peak in 840 cm -1) is at 1150cm -1 and 1259cm -1.
The reaction process of synthesizing acrylic acid by CO 2 and ethylene is carried out in an autoclave, 4.3g of the prepared catalyst and 120mL of acetonitrile are added into the autoclave, then raw material gas carbon dioxide and ethylene are introduced, the mole ratio of the carbon dioxide to the ethylene is 1.7, and the catalyst accounts for 5 percent of the total amount of the reaction system. The reaction temperature is 70 ℃, the reaction pressure is 5.0MPa, and the yield of the acrylic acid is 5.34% after 7h of reaction.
Example 2
(1) Firstly, dissolving tetramethyl urea in toluene, wherein the volume ratio of toluene to tetramethyl urea is 9:1, adding phosphorus oxychloride under the protection of nitrogen, reacting for 8 hours at room temperature, adding cyclohexylamine, reacting for 25 hours at room temperature, adding distilled water, the volume ratio of distilled water to toluene is 2:1, continuously reacting for 4 hours, and standing for layering for 40 minutes. NaOH is added into the lower layer liquid, and the mol ratio of NaOH to phosphorus oxychloride is 4:1. Drying the upper layer liquid after layering, distilling, and collecting distillate at 128-132 deg.C under 32 mmHg;
(2) And (3) dissolving the distillate in acetonitrile, wherein the volume ratio of the distillate to the acetonitrile is 1:20, adding a mixed solution of methyl iodide and acetonitrile under the cooling of an ice water bath and the protection of nitrogen, wherein the volume ratio of the methyl iodide to the acetonitrile is 1:5, the volume ratio of the acetonitrile to the mixed solution of the methyl iodide and the acetonitrile is 4:1, and controlling the flow rate to 7mL/min. After the system is restored to room temperature, stirring and reacting for 36h, distilling at normal pressure after the reaction is finished, evaporating the solvent at 100 ℃, and washing the residual liquid with ethyl acetate for three times. Removing ethyl acetate by vacuum suction filtration after washing to obtain 1.1.3.3-tetramethyl-2-cyclohexylguanidine salt of I -;
(3) And (3) carrying out anion exchange on Pb salt with anions of CH 3COO- and organic guanidine salt with anions of I -, wherein the molar ratio of the organic guanidine salt with anions of I - to the Pb salt with anions of CH 3COO- is 1:1, reacting for 5 hours at room temperature, adding methylene dichloride after the reaction to separate an oil layer, washing with distilled water, drying with anhydrous sodium sulfate, removing the anhydrous sodium sulfate by suction filtration, and distilling at normal pressure to remove a solvent to obtain the catalyst.
The reaction process of synthesizing acrylic acid by CO 2 and ethylene is carried out in an autoclave, 4.3g of the prepared catalyst and 120mL of acetonitrile are added into the autoclave, then raw material gas carbon dioxide and ethylene are introduced, the mole ratio of the carbon dioxide to the ethylene is 1.7, and the catalyst accounts for 5.5 percent of the total amount of the reaction system. The reaction temperature is 100 ℃, the reaction pressure is 5.0MPa, and the yield of the acrylic acid is 5.16% after 7 hours of reaction.
Example 3
(1) Firstly, dissolving tetramethyl urea in toluene, wherein the volume ratio of toluene to tetramethyl urea is 16:1, adding phosphorus oxychloride under the protection of nitrogen, reacting for 4 hours at room temperature, adding cyclohexylamine, reacting for 25 hours at room temperature, adding distilled water, the volume ratio of distilled water to toluene is 2:1, and standing for layering for 10 minutes after continuing to react for 12 hours. NaOH is added into the lower layer liquid, and the mol ratio of NaOH to phosphorus oxychloride is 8:1. Drying the upper layer liquid after layering, distilling, and collecting distillate at 128-132 deg.C under 32 mmHg;
(2) And (3) dissolving the distillate in acetonitrile, wherein the volume ratio of the distillate to the acetonitrile is 1:15, adding a mixed solution of methyl iodide and acetonitrile under the cooling of an ice water bath and the protection of nitrogen, wherein the volume ratio of the methyl iodide to the acetonitrile is 1:5, the volume ratio of the acetonitrile to the mixed solution of the methyl iodide and the acetonitrile is 2:1, and controlling the flow rate to be 1mL/min. After the system is restored to room temperature, stirring and reacting for 24 hours, distilling at normal pressure after the reaction is finished, evaporating the solvent at 50 ℃, and washing the residual liquid with ethyl acetate for three times. Removing ethyl acetate by vacuum suction filtration after washing to obtain 1.1.3.3-tetramethyl-2-cyclohexylguanidine salt of I -;
(3) The sodium salt with the anion of BF 4 - and the 1.1.3.3-tetramethyl-2-cyclohexylguanidine salt with the anion of I - are subjected to anion exchange, the molar ratio of the organic guanidine salt with the anion of I - to the non-I - metal salt is 1:2, the reaction is carried out for 0.5h at room temperature, methylene dichloride is added after the reaction to separate an oil layer, then distilled water is used for washing, anhydrous sodium sulfate is used for drying, the anhydrous sodium sulfate is removed by suction filtration, and the solvent is removed by normal pressure distillation, so that the catalyst is obtained.
The reaction process of synthesizing acrylic acid by CO 2 and ethylene is carried out in an autoclave, 4.3g of the prepared catalyst and 120mL of acetonitrile are added into the autoclave, then raw material gas carbon dioxide and ethylene are introduced, the mole ratio of the carbon dioxide to the ethylene is 1.7, and the catalyst accounts for 6.5 percent of the total amount of the reaction system. The reaction temperature is 130 ℃, the reaction pressure is 5.0MPa, and the yield of the acrylic acid is 5.18% after 7h of reaction.
Example 4
The difference from example 1 is that: toluene was used for solvent A, B, C to prepare the catalyst. The yield of acrylic acid was 3.98%.
Example 5
The difference from example 1 is that: tetrahydrofuran was used for solvent A, B, C to prepare the catalyst. The yield of acrylic acid was 3.76%.
Example 6
The difference from example 1 is that: benzene is used as solvent A, B, C to prepare the catalyst. The yield of acrylic acid was 3.58%.
Example 7
The difference from example 1 is that: the solvent A is subjected to water removal and deoxidization treatment, and particularly, the solvent is distilled out after refluxing for 3 hours in the presence of metallic sodium and benzophenone, so as to prepare the catalyst. The yield of acrylic acid was 5.76%.
Example 8
The difference from example 1 is that: the alkylamine is cyclopentylamine, and the catalyst is prepared. The yield of acrylic acid was 5.03%.
Example 9
The difference from example 1 is that: the alkylamine is butylamine to prepare the catalyst. The yield of acrylic acid was finally 4.69%.
Example 10
The difference from example 1 is that: in the non-I - metal salt, the anion is BF 4 -, and the metal ion is Pb 2+, so that the catalyst is prepared. The yield of acrylic acid was finally 4.09%.
Example 11
The difference from example 1 is that: in the non-I - metal salt, the anion is CH 3CH(OH)COO-, and the metal ion is Zn 2+, so that the catalyst is prepared. The yield of acrylic acid was 3.59%.
Example 12
The difference from example 1 is that: in the non-I - metal salt, the anion is N (CN) 2 -, and the metal ion is Mg 2+, so that the catalyst is prepared. The yield of acrylic acid was 3.03%.
Comparative example 1
The difference from example 1 is that: the catalyst is prepared by directly mixing tetramethyl urea, solvent A, phosphorus oxychloride, alkylamine, distilled water and sodium hydroxide according to the same proportion. The yield of acrylic acid was finally 1.02%.
Comparative example 2
The difference from example 1 is that: the catalyst is prepared by adopting dodecyl primary amine as alkylamine. The yield of acrylic acid was 0.98%.
Comparative example 3
The difference from example 1 is that: the methyl iodide is replaced by methyl chloride to prepare the catalyst. The yield of acrylic acid was 2.56%.
Comparative example 4
The difference from example 1 is that: and (3) directly mixing methyl iodide in the step (2) with distillate to prepare the catalyst. The yield of acrylic acid was finally 1.03%.
Comparative example 5
The difference from example 1 is that: step (3) is omitted, i.e., no anion exchange is performed, to prepare the catalyst. The yield of acrylic acid was 2.48%.
Claims (24)
1. The preparation method of the catalyst for synthesizing the acrylic acid is characterized by comprising the following steps:
(1) Dissolving tetramethylurea in a solvent A, adding phosphorus oxychloride under the protection of nitrogen for reaction, then adding alkylamine for reaction, then adding water for continuous reaction, standing for layering after the reaction, adding NaOH into a lower layer solution, and distilling an upper layer solution after layering to obtain distillate;
(2) Dissolving distillate into a solvent B, adding a mixed solution of methyl iodide and the solvent C under the protection of ice-water bath and nitrogen, continuing to react after the system is restored to room temperature, distilling at normal pressure after the reaction, and washing residual liquid to obtain I - ion organic guanidine salt;
(3) Anion exchange is carried out on non-I - ion metal salt and organic guanidine salt of I -, then dichloromethane is added, an oil layer is separated, and the catalyst is obtained through washing, drying and distillation.
2. The method of claim 1, wherein: the solvent A in the step (1) is at least one of acetonitrile, benzene, toluene and tetrahydrofuran, preferably toluene.
3. The method of claim 2, wherein: and (3) carrying out water removal and deoxidization treatment on the solvent A, specifically, refluxing for 3 hours in the presence of metallic sodium and benzophenone, and then evaporating the solvent.
4. The method of claim 1, wherein: the volume ratio of the solvent A to the tetramethylurea in the step (1) is 5-20:1, preferably 8-16:1.
5. The method of claim 1, wherein: the molar ratio of the tetramethylurea to the phosphorus oxychloride in the step (1) is 0.5:1-1:5, preferably 0.5:1-1:3.
6. The method of claim 1, wherein: and (2) adding phosphorus oxychloride under the protection of nitrogen, wherein the reaction time is 2-15 h, and preferably 4-14 h.
7. The method of claim 1, wherein: the alkylamine in the step (1) is at least one of C4-C6 alkylamines, preferably at least one of butylamine, pentylamine, hexylamine, cyclopentylamine or cyclohexylamine, more preferably cyclopentylamine or cyclohexylamine.
8. The method of claim 1, wherein: the molar ratio of the alkylamine to the tetramethylurea in the step (1) is 1:0.5-1:3, preferably 1:0.7-1:2; after the addition of the alkylamine, the reaction time is 20 to 80 hours, preferably 25 to 60 hours.
9. The method of claim 1, wherein: the volume ratio of the distilled water to the solvent A added in the step (1) is 2.5:1-0.7:1, preferably 2:1-1:1; the reaction time is 2 to 15 hours, preferably 4 to 12 hours after the addition.
10. The method of claim 1, wherein: the standing delamination time in the step (1) is 5-60 min, preferably 10-40 min.
11. The method of claim 1, wherein: the molar ratio of NaOH to phosphorus oxychloride in the step (1) is 10:1-3:1, preferably 8:1-4:1.
12. The method of claim 1, wherein: and (3) taking distillate at 128-132 ℃ from the layered upper layer liquid in the step (1) under the condition of 30-32 mmHg.
13. The method of claim 1, wherein: the solvent B in the step (2) is at least one of acetonitrile, benzene, toluene or tetrahydrofuran, preferably acetonitrile.
14. The method of claim 1, wherein: the volume ratio of the solvent B to the distillate in the step (2) is 30:1-10:1, preferably 20:1-15:1.
15. The method of claim 1, wherein: the solvent C in the step (2) is at least one of acetonitrile, benzene, toluene or tetrahydrofuran, preferably benzene.
16. The method of claim 1, wherein: the volume ratio of the methyl iodide to the solvent C in the step (2) is 1:5-1:20, preferably 1:10-1:17; the volume ratio of the solvent B to the mixed solution of methyl iodide and the solvent C is 1-5:1, preferably 1.5-4:1; when the mixed solution of methyl iodide and the solvent C is added, the flow rate is controlled to be 0.5-10 mL/min, preferably 1-7 mL/min.
17. The method of claim 1, wherein: step (2), after the system is restored to room temperature, continuing to react for 24-36h; performing atmospheric distillation at 50-150deg.C after reaction; the residual liquid is washed by ethyl acetate for 3 to 5 times, and the ethyl acetate is removed by vacuum suction filtration after washing.
18. The method of claim 1, wherein: the non-I - ion metal salt in the step (3) is selected from at least one of BF 4 -、PF6 -、CH3COO-、CH3CH(OH)COO- or N (CN) 2 - metal salt, preferably a metal salt with PF 6 - anion; the metal ion in the metal salt is at least one of Na +,Mg2+,Zn2+,Pb2+, ca 2+, and the like, and preferably Na + or Pb 2+.
19. A process as claimed in claim 1 or 18, wherein: the molar ratio of the organic guanidine salt of the I - ion to the metal salt of the non-I - ion in the step (3) is 1:1-1:3, preferably 1:1-1:2.
20. The method of claim 1, wherein: the ion exchange reaction in the step (3) is carried out for 0.5 to 5 hours at room temperature, after the reaction is finished, methylene dichloride is added, and then an oil layer is separated; distilled water is adopted for washing, anhydrous sodium sulfate is adopted for drying, and the solvent is distilled off at normal pressure to obtain the catalyst.
21. A catalyst for synthesizing acrylic acid is characterized by being prepared by the method.
22. A method for synthesizing acrylic acid is characterized in that: acrylic acid is directly synthesized by using CO 2 and ethylene as raw materials and acetonitrile as a solvent and adopting the catalyst of claim 21.
23. The method of claim 22, wherein: the mol ratio of ethylene to carbon dioxide is 1:1-1:10, preferably 1:3-1:8; the reaction temperature is 50-150 ℃, preferably 70-130 ℃; the reaction pressure is 0.5 to 6.0MPa, preferably 1.0 to 5.5MPa.
24. The method of claim 22, wherein: the catalyst accounts for 5 to 7.5 percent of the total amount of the reaction system; the ratio of the catalyst to the acetonitrile is 2-4.5 g to 100-200 mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211602171.2A CN118179589A (en) | 2022-12-14 | 2022-12-14 | Catalyst for synthesizing acrylic acid and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211602171.2A CN118179589A (en) | 2022-12-14 | 2022-12-14 | Catalyst for synthesizing acrylic acid and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118179589A true CN118179589A (en) | 2024-06-14 |
Family
ID=91404814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211602171.2A Pending CN118179589A (en) | 2022-12-14 | 2022-12-14 | Catalyst for synthesizing acrylic acid and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118179589A (en) |
-
2022
- 2022-12-14 CN CN202211602171.2A patent/CN118179589A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1034531A (en) | The method of dehydrogenating of cyclonene | |
| CN101367732A (en) | Process and apparatus for preparing diethyl carbonate | |
| CN102452934B (en) | Preparation method of sec-butyl acetate | |
| CN110818566A (en) | Method for preparing cyclopentanol from cyclopentene | |
| CN109794285B (en) | Catalyst for preparing glycolic acid by carbonylation of formaldehyde and preparation method and application thereof | |
| CN106478586B (en) | Synthesis process of ethylene carbonate | |
| CN1621405A (en) | Process for preparing caprolactam by cyclohexanone-oxime gas phase rearrangement | |
| CN118179589A (en) | Catalyst for synthesizing acrylic acid and preparation method and application thereof | |
| CN109942370B (en) | Green and efficient methallyl alcohol synthesis process | |
| CN1216877C (en) | Method of preparing gamma-butyrolactone and/or 1,4-butanediol using chromium less catalyst | |
| CN115141165A (en) | Co-production method and co-production system of maleic anhydride and succinic anhydride | |
| CN102001930B (en) | Method for purifying chloroacetic acid by catalytic hydrogenolysis in chloroacetic acid production and application thereof | |
| CN111393402B (en) | N & lt/EN & gt acid/quaternary ammonium salt composite catalytic CO 2 Method for preparing cyclic carbonate by cycloaddition with epoxide | |
| CN110922328B (en) | Method for treating heavy components in crude isooctanoic acid product | |
| CN1726203B (en) | Process for producing alkylene carbonate | |
| CN109499618B (en) | Catalyst for preparing benzoylformic acid and ester compounds thereof, and preparation method and application thereof | |
| CN102321054B (en) | Preparation method of tetrahydrofuran-3-ketone compound | |
| CN1810750A (en) | Heteropoly acid catalyzed process to eliminate micro aldehyde group from 1,3-propylene glycol | |
| JPH0248541A (en) | Production of terpene alcohol | |
| CN1693302A (en) | Process for producing methyl carbamate by low pressure solvation homogeneous phase reaction | |
| CN101463016A (en) | Method for synthesizing 2,6-dimethyl piperazine | |
| CN116328825B (en) | Catalyst, preparation method thereof and method for preparing methyl 3-methoxypropionate by using catalyst to catalyze methanol and methyl acetate | |
| CN109824483B (en) | New method for preparing nopol | |
| CN113461552B (en) | Preparation method of N, N-dimethyl monoethanolamine | |
| CN112624905B (en) | Preparation method of novel tricyclodecanediol, product and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |