CN114292168A - Method for preparing acetone by using byproducts in triacetonamine synthesis process - Google Patents
Method for preparing acetone by using byproducts in triacetonamine synthesis process Download PDFInfo
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- CN114292168A CN114292168A CN202111447871.4A CN202111447871A CN114292168A CN 114292168 A CN114292168 A CN 114292168A CN 202111447871 A CN202111447871 A CN 202111447871A CN 114292168 A CN114292168 A CN 114292168A
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- acid
- acetone
- triacetonamine
- catalyst
- byproducts
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000000034 method Methods 0.000 title claims abstract description 80
- 239000006227 byproduct Substances 0.000 title claims abstract description 70
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 230000015572 biosynthetic process Effects 0.000 title claims description 30
- 238000003786 synthesis reaction Methods 0.000 title claims description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000003377 acid catalyst Substances 0.000 claims description 21
- 239000002808 molecular sieve Substances 0.000 claims description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 19
- 230000002378 acidificating effect Effects 0.000 claims description 16
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 229910021536 Zeolite Inorganic materials 0.000 claims description 14
- 239000010457 zeolite Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 11
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 7
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 claims description 7
- PIFBMJMXJMZZRG-UHFFFAOYSA-N 2,2,4,6,6-pentamethyl-1,5-dihydropyrimidine Chemical compound CC1=NC(C)(C)NC(C)(C)C1 PIFBMJMXJMZZRG-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 6
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 6
- 229930193351 phorone Natural products 0.000 claims description 6
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 claims description 5
- 239000003729 cation exchange resin Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- CQTRUFMMCCOKTA-UHFFFAOYSA-N diacetoneamine hydrogen oxalate Natural products CC(=O)CC(C)(C)N CQTRUFMMCCOKTA-UHFFFAOYSA-N 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 4
- 150000004692 metal hydroxides Chemical class 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000002841 Lewis acid Substances 0.000 claims description 2
- 229910003112 MgO-Al2O3 Inorganic materials 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910006069 SO3H Inorganic materials 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- -1 amine salt Chemical class 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000005915 ammonolysis reaction Methods 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910021523 barium zirconate Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N chromium(III) oxide Inorganic materials O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 150000007517 lewis acids Chemical class 0.000 claims description 2
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims 2
- 238000010979 pH adjustment Methods 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 abstract description 5
- 230000008929 regeneration Effects 0.000 abstract description 5
- 238000011069 regeneration method Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 4
- 239000011973 solid acid Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000004817 gas chromatography Methods 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- 150000003384 small molecules Chemical class 0.000 description 4
- 239000013638 trimer Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XQDIZYUSQLQEHV-UHFFFAOYSA-N CC(C)=O.CC(C)=O.CC(C)=O Chemical compound CC(C)=O.CC(C)=O.CC(C)=O XQDIZYUSQLQEHV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- BCDGQXUMWHRQCB-UHFFFAOYSA-N glycine methyl ketone Natural products CC(=O)CN BCDGQXUMWHRQCB-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000001648 tannin Substances 0.000 description 1
- 235000018553 tannin Nutrition 0.000 description 1
- 229920001864 tannin Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing acetone by utilizing byproducts in the process of synthesizing triacetonamine, which not only effectively utilizes the byproducts, but also synthesizes triacetonamine by utilizing the regenerated acetone, so that raw materials for synthesizing triacetonamine are changed into single acetone from acetone and various byproducts, technological parameters are optimized aiming at the single raw material, and the yield of the whole process is greatly improved; the problems of poor selectivity and low yield caused by the process of directly recycling the byproduct to the raw material acetone to synthesize triacetonamine are avoided, the yield is finally improved, and the comprehensive production cost is reduced; the method uses the solid acid catalyst even without the catalyst in the cyclic regeneration process of the invalid by-products, does not need the operation process of generating three wastes such as neutralization and the like, and is more environment-friendly.
Description
Technical Field
The invention relates to a method for improving a triacetonamine synthesis process, in particular to a method for preparing acetone by using a byproduct in the Triacetonamine (TAA) synthesis process.
Background
TAA is a key intermediate for synthesizing hindered amine light stabilizer and antioxidant, and in addition, TAA can be used as lubricant, fuel additive and physiological active substance.
The main synthesis processes of TAA include direct method and indirect method. The synthesis process of TAA uses acetone and ammonia as raw materials, and the synthesis is carried out under the action of homogeneous acidic catalyst (such as ammonium salt) or heterogeneous catalyst (such as acidic ion exchange resin). Typical by-products formed by the TAA synthesis process include acetone dimer, acetone trimer, diacetone amine, acetonine, and acetone formed from 3, 4-dihydro-2H-pyran DHP or phorone, isophorone, etc. The by-products separated in the course of refining the crude TAA are generally mixed with acetone as raw materials for synthesizing the TAA, and are circularly applied to the next batch of synthesis process, or the thermodynamic and kinetic conditions of the reaction for converting each by-product component to the TAA are matched at the same time because the single condition of the TAA synthesis process cannot be optimized, so that the utilization rate of the by-products is maximized, the by-products are accumulated and used as fuel oil, and the by-products are used inefficiently.
Patent US3943139 and patent US3960875 respectively disclose methods for synthesizing TAA from raw materials synthesized from acetonin, phorone and diacetone alcohol with good yield. However, the synthesis and separation of acetonine, phorone and diacetone alcohol are difficult, the steps are long, and the cost is high, so that the industrial production is difficult to realize.
Patent CN108383704 discloses a method for preparing acetone by hydrolyzing TAA by-product in the presence of alkaline catalyst, the catalyst used is generally homogeneous catalyst such as hydroxide, carbonate or organic ammonium salt dissolved in water or acetone, the homogeneous catalyst is difficult to separate and recover, and simultaneously generates a large amount of high saline-alkali waste water, which is difficult to treat.
The prior art can not effectively regenerate the ineffective by-product formed in the synthesis process of triacetonamine and convert the ineffective by-product into reaction raw material acetone required by preparing a product TAA, thereby reducing the consumption of the raw material acetone; and the used alkaline catalyst can cause alkali and energy consumption and simultaneously can generate high-saline-alkali organic wastewater which is difficult to treat, thereby causing environmental pollution.
Disclosure of Invention
The invention overcomes the problems that the invalid by-products can not be converted into raw material acetone, the utilization rate of the invalid by-products is low, and the 'three wastes' generated in the cyclic regeneration process can cause industrial pollution, and the like, and provides the method for preparing the acetone by using the by-products in the TAA synthesis process.
A method for preparing acetone by using byproducts in the TAA synthesis process comprises the following specific process steps:
(a) adding a byproduct formed in the TAA synthesis process into the autoclave;
(b) adding water into the autoclave, wherein the weight of the water is 10-200% of the weight of the material to be treated, preferably 15-150% of the weight of the material to be treated, and more preferably 10-100% of the weight of the material to be treated;
(c) starting the reaction kettle and stirring, and heating the kettle to 60-150 ℃, preferably to 60-140 ℃, and more preferably to 90-140 ℃;
(d) stirring for 1 to 12 hours, preferably 3 to 10 hours, more preferably 3 to 9 hours;
(e) after the reaction is finished, the regenerated acetone is directly put into a main production line of the TAA to be used as a synthetic raw material, and the reaction kettle is replenished with water and then enters the next batch of regenerated acetone operation.
Furthermore, the by-product in step (a) of the present invention is a series of by-products generated during the synthesis of TAA by direct method (one-step method) or indirect method (two-step method) using acetone as raw material.
Further, the series of by-products includes at least mesityl oxide, acetonine, and phorone.
Further, the series of by-products also comprise diacetone alcohol, diacetone amine, isophorone and 3, 4-dihydro-2H-pyran (DHP).
Further, the series of byproducts also comprises acetone dimers, acetone trimers and acetone ammonolysis products of the dimers or the acetone trimers, wherein the acetone dimers, the acetone trimers, the acetone diacetone, the acetone amine, the acetone tannin, the 3, 4-dihydro-2H-pyran (DHP) or the phorone.
Further, the step (b) of the present invention further comprises adding a catalyst; step (e) of the present invention further comprises a post-treatment step of the catalyst added in step (b) before the regenerated acetone is fed into the main production line of TAA as a synthesis raw material.
Further, the weight of the catalyst is 0.2-20% of the weight of the material to be treated, preferably 0.3-15% of the weight of the material to be treated, and more preferably 0.5-10% of the weight of the material to be treated.
Further, the catalyst comprises an acidic catalyst.
Further, the acid catalyst is a homogeneous acid catalyst or a heterogeneous acid catalyst.
Further, the homogeneous acid catalyst is protonic acid or Lewis acid substances.
Further, the protonic acid is selected from: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, organic carboxylic acids (R)1COOH), organic sulfonic acid (R)1SO3H) And one of ammonium salt or amine salt of the above acid, wherein R1Selected from: saturated, unsaturatedBranched, unbranched, closed-ring, open-chain aliphatic, aromatic, substituted and unsubstituted hydrocarbon radicals, said substituted hydrocarbon radicals being hydrocarbon radicals substituted by heteroatoms, in particular by groups selected from: hydrocarbyl substituted by one or more groups selected from-OH, -NH, -CN, alkoxy and halogen, preferably by one or more halogen groups, particularly preferably by a group selected from: F. the hydrocarbon group substituted with one or more groups selected from Cl, Br and I, most particularly preferably means a hydrocarbon group substituted with a group selected from: and a hydrocarbon group substituted with one or more groups selected from F and Cl.
Further, the organic sulfonic acid is methanesulfonic acid or p-toluenesulfonic acid.
Further, the Lewis acid-type substance comprises a halide.
Further, the halide is selected from: InCl3，FeCl3And ZnCl2One or a combination of two or more of them.
Further, the heterogeneous acid catalyst is selected from the group consisting of: metal oxide and its doped modified body, composite oxide, heteropoly acid, synthetic molecular sieve, ion exchange resin, silica, alumina, hydrotalcite and active carbon loaded with acidic substance, and one of the doped body of metal hydroxide and metal hydroxide, aluminosilicate, solid organic sulfonic acid, solid organic carboxylic acid, metal halide, organic ammonium salt and super strong acid.
Further, the metal oxide is selected from: one or more of molybdenum trioxide, aluminum oxide, titanium dioxide and ferric trioxide.
Further, the composite oxide is selected from: WO3-ZrO2、CeO2-Cr2O3、MgO-Al2O3、MgO-CeO2And MgO-BaZrO3One or a combination of two or more of them.
Further, the ion exchange resin is a cation exchange resin, preferably an acidic cation exchange resin.
Further, the acidic cation exchange resin is selected from the group consisting of: one or a combination of two or more of a sulfonic acid resin, a fluorosulfonic acid resin, an alkylsulfonic acid resin, and a phosphoric acid resin, preferably a sulfonic acid resin or a fluorosulfonic acid resin.
Further, the synthetic molecular sieve comprises a zeolite-type molecular sieve.
Further, the zeolite-type molecular sieve comprises a Y-type zeolite molecular sieve.
Further, the Y-type zeolite molecular sieve is NH4 +Ammonium type Y zeolite molecular sieve or H proton Y zeolite molecular sieve.
Further, the homogeneous acid catalyst is preferably one of sulfuric acid, phosphoric acid, methanesulfonic acid and p-toluenesulfonic acid.
Further, the heterogeneous acid catalyst is preferably sulfonic acid resin, fluorosulfonic acid resin, NH4 +One of ammonium type Y zeolite and H proton type Y zeolite.
Further, the post-treatment process comprises the following steps: for the homogeneous acid catalyst, an alkaline substance is used for neutralizing and destroying the homogeneous acid catalyst to inactivate the homogeneous acid catalyst, wherein the alkaline substance comprises an alkali metal hydroxide or an alkaline earth metal hydroxide with alkalinity larger than that of ammonia water, the alkaline substance is added to adjust the pH, and the pH is controlled within the range of 6-8, preferably 6.5-7.5; in the case of heterogeneous acid catalysts, a filter is used to filter out the heterogeneous acid catalyst.
In another aspect of the present invention, there is provided a method for preparing TAA using acetone prepared by the above method using a byproduct from the TAA synthesis process.
The invention idea of the application is to carry out a technical improvement on the existing TAA synthesis process. Firstly, in the prior art, "acetone + various byproducts" are mostly used for synthesizing the TAA, while in the application, "acetone + various byproducts" is changed into single acetone, and then the TAA is synthesized; secondly, in the prior art, basic catalysts are mostly used for catalyzing and hydrolyzing ineffective byproducts, but on the basis that the acidic catalysts are proved to be capable of effectively catalyzing the hydrolysis process of the ineffective byproducts, the method specifically indicates that the solid acid catalysts can complete the cyclic regeneration of the ineffective byproducts with the same efficiency, and do not need to perform the operation process of generating three wastes such as neutralization and the like, so that the method is more environment-friendly. At the same time, we have found, more surprisingly, that this process of regenerating the ineffective by-products can be carried out even in the absence of a catalyst.
The method utilizes the byproduct obtained in the TAA synthesis process to synthesize acetone, so that the byproduct is effectively utilized, and the regenerated acetone is used for synthesizing the TAA, so that the raw material for synthesizing the TAA is changed from acetone and multiple byproducts into single acetone, the technological parameters are optimized aiming at the single raw material, and the yield of the whole process is greatly improved; the problems of poor selectivity and low yield caused by directly recycling the byproduct in the process of synthesizing TAA by using acetone as the raw material are avoided, the yield is finally improved, and the comprehensive production cost is reduced; the method uses the solid acid catalyst even without the catalyst in the cyclic regeneration process of the invalid by-products, does not need the operation process of generating three wastes such as neutralization and the like, and is more environment-friendly.
Detailed Description
In order to clearly understand the technical contents of the present invention, the following examples are given in detail for the purpose of better understanding the contents of the present invention and are not intended to limit the scope of the present invention.
The embodiments 1 to 4 of the invention prove that the by-products can be efficiently hydrolyzed under the condition of an acid catalyst even without the catalyst, and can be regenerated into raw material acetone or micromolecular acetone addition compound, the preparation process is simple, the cost is low, the conversion rate is high, and particularly, the invention proves that the solid acid catalyst can complete the cyclic regeneration of ineffective by-products with the same efficiency, and the operation process of generating three wastes such as neutralization and the like is not needed, so that the invention is more environment-friendly.
Example 1
1.1 preparation method
(a) Adding 300g of by-product into the autoclave;
(b) adding 300g of water into the autoclave;
(c) starting the autoclave to stir, and heating the autoclave to 100 ℃;
(d) keeping the temperature of the kettle at 100 ℃, and stirring for 8 hours;
(e) after the reaction is finished, sampling and analyzing, and distilling out acetone and small molecule acetone addition compound to be recycled.
1.2 gas chromatography analysis of by-products
The composition of the by-products to be treated and after treatment is analyzed by gas chromatography as in table 1 ("NI" is unknown).
TABLE 1
Example 2
2.1 preparation method
(a) Adding 300g of by-product into the autoclave;
(b) adding 15g of phosphoric acid and 300g of water into an autoclave;
(c) starting the autoclave to stir, and heating the autoclave to 95 ℃;
(d) keeping the temperature of the kettle at 95 ℃, and stirring for 6 hours;
(e) after the reaction, sampling and analyzing, and distilling out acetone and small molecule acetone addition compound to be recovered and reused by using 12.2g of sodium hydroxide.
2.2 gas chromatography analysis of by-products
The composition of the by-products to be treated and after treatment is analyzed by gas chromatography as in table 2 ("NI" is unknown).
TABLE 2
Example 3
3.1 preparation method
(a) Adding 300g of by-product into the autoclave;
(b) 30g of p-toluenesulfonic acid and 300g of water are added into an autoclave;
(c) starting the autoclave to stir, and heating the autoclave to 95 ℃;
(d) keeping the temperature of the kettle at 95 ℃, and stirring for 8 hours;
(e) after the reaction, sampling and analyzing, and distilling out acetone and small molecule acetone addition compound to be recovered and reused by 13.1g of sodium hydroxide.
3.2 gas chromatography analysis of by-products
The composition of the by-products to be treated and after treatment is analyzed by gas chromatography as in table 3 ("NI" is unknown).
TABLE 3
Example 4
4.1 preparation method
(a) 300g of by-product was added to the autoclave and the composition of the by-product was analyzed by gas chromatography as in Table 4 ("NI" is unknown);
(b) adding 300g of catalyst HND-58030 g and water into an autoclave;
(c) starting the autoclave to stir, and heating the autoclave to 105 ℃;
(d) keeping the temperature of the kettle at 105 ℃, and stirring for 8 hours;
(e) after the reaction is finished, sampling and analyzing, filtering the catalyst, and distilling out acetone and small molecule acetone addition compound to be recycled and reused.
4.2 gas chromatography analysis of by-products
The composition of the by-products to be treated and after treatment is analyzed by gas chromatography as in table 4 ("NI" is unknown).
TABLE 4
Claims (10)
1. A method for preparing acetone by using byproducts in the triacetonamine synthesis process comprises the following specific process steps:
(a) adding a byproduct formed in the triacetonamine synthesis process into the high-pressure kettle;
(b) adding water into the autoclave, wherein the weight of the water is 10-200% of the weight of the material to be treated, preferably 15-150% of the weight of the material to be treated, and more preferably 10-100% of the weight of the material to be treated;
(c) starting the reaction kettle and stirring, and heating the kettle to 60-150 ℃, preferably to 60-140 ℃, and more preferably to 90-140 ℃;
(d) stirring for 1 to 12 hours, preferably 3 to 10 hours, more preferably 3 to 9 hours;
(e) after the reaction is finished, directly putting the regenerated acetone into a main production line of triacetonamine as a synthetic raw material, and feeding the regenerated acetone into the next batch of regenerated acetone operation after water is supplemented to a reaction kettle;
the by-products in step (a) are a series of by-products generated in the process of synthesizing triacetonamine by a direct method or an indirect method by using acetone as a raw material, preferably, the series of by-products at least comprise mesityl oxide, acetonine and phorone, more preferably, the series of by-products also comprise diacetone alcohol, diacetone amine, isophorone and 3, 4-dihydro-2H-pyran, and particularly preferably, the series of by-products also comprise diacetone, tripolymer and ammonolysis products of the diacetone or the tripolymer, wherein the diacetone alcohol, the diacetone amine, the acetonine, the 3, 4-dihydro-2H-pyran or the phorone forms acetone.
2. The method for preparing acetone from the byproducts generated in the process of synthesizing triacetonamine according to claim 1, wherein the step (b) further comprises adding a catalyst; the step (e) also comprises a post-treatment step of the catalyst added in the step (b) before the regenerated acetone is put into a main production line of triacetonamine as a synthetic raw material.
3. The method for preparing acetone from the byproducts in the triacetonamine synthesis process of claim 2, wherein the weight of the catalyst is 0.2-20% of the weight of the material to be treated, preferably 0.3-15% of the weight of the material to be treated, and more preferably 0.5-10% of the weight of the material to be treated.
4. The method for preparing acetone from the byproducts of the triacetonamine synthesis process of claim 2, wherein the catalyst comprises an acidic catalyst, and the acidic catalyst is a homogeneous acidic catalyst or a heterogeneous acidic catalyst; the homogeneous phase acid catalyst is protonic acid or Lewis acid substance; the protonic acid is selected from: hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, organic carboxylic acids (R)1COOH), organic sulfonic acid (R)1SO3H) And one of ammonium salt or amine salt of the above acid, wherein R1Selected from: one or a combination of more than two of saturated, unsaturated, branched, unbranched, closed-ring, open-chain aliphatic, aromatic, substituted and unsubstituted hydrocarbon groups, wherein the organic sulfonic acid is methane sulfonic acid or p-toluene sulfonic acid; the Lewis acid-type substance comprises a halide selected from the group consisting of: InCl3，FeCl3And ZnCl2One or a combination of two or more of them.
5. The method for preparing acetone from the byproducts of the triacetonamine synthesis process of claim 4, wherein the heterogeneous acid catalyst is selected from the group consisting of: metal oxide and doped modified body of metal oxide, composite oxide, heteropoly acid, synthetic molecular sieve, ion exchange resin, silica loaded with acidic substance, alumina, hydrotalcite, active carbon, metal hydroxide and one of the doped body of metal hydroxide, aluminosilicate, solid organic sulfonic acid, solid organic carboxylic acid, loaded metal halide, loaded organic ammonium salt and solid super strong acid; the metal oxide is selected from: one or more of molybdenum trioxide, aluminum oxide, titanium dioxide and ferric trioxide, wherein the composite oxide is selected from the group consisting of: WO3-ZrO2、CeO2-Cr2O3、MgO-Al2O3、MgO-CeO2And MgO-BaZrO3One or a combination of two or more of (a) and (b), wherein the ion exchange resin is an acidic cation exchange resin selected from the group consisting of: sulfonic acid resin,One or more of fluorosulfonic acid resin, alkylsulfonic acid resin and phosphoric acid resin, preferably, the acidic cation exchange resin is sulfonic acid resin or fluorosulfonic acid resin; the synthetic molecular sieve comprises a zeolite type molecular sieve, the zeolite type molecular sieve comprises a Y type zeolite molecular sieve, and the Y type zeolite molecular sieve is NH4 +Ammonium type Y zeolite molecular sieve or H proton Y zeolite molecular sieve.
6. The method for preparing acetone from the byproducts generated in the triacetonamine synthesis process of claim 4, wherein the homogeneous acidic catalyst is selected from the group consisting of: one of sulfuric acid, phosphoric acid, methanesulfonic acid and p-toluenesulfonic acid.
7. The method for preparing acetone from the byproducts of the triacetonamine synthesis process of claim 5, wherein the heterogeneous acidic catalyst is an ion exchange resin or a synthetic molecular sieve.
8. The method for preparing acetone from the byproducts of the triacetonamine synthesis process of claim 5, wherein the heterogeneous acid catalyst is selected from the group consisting of: sulfonic acid resin, fluorosulfonic acid resin, NH4 +One of an ammonium type Y zeolite molecular sieve and an H proton type Y zeolite molecular sieve.
9. The method for preparing acetone from the byproducts generated in the triacetonamine synthesis process according to claim 2, wherein the post-treatment step comprises: for the homogeneous acid catalyst, a basic substance is used for neutralizing and destroying the homogeneous acid catalyst so as to deactivate the homogeneous acid catalyst; the alkaline substance comprises alkali metal hydroxide or alkaline earth metal hydroxide with alkalinity larger than that of ammonia water, the alkaline substance is added for pH adjustment, and the pH is controlled within the range of 6-8; in the case of heterogeneous acid catalysts, a filter is used to filter out the heterogeneous acid catalyst.
10. A method for preparing triacetonamine from acetone produced by the method of claim 1 using a by-product of the triacetonamine synthesis process.
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| CN108383704A (en) * | 2018-05-01 | 2018-08-10 | 衡水凯亚化工有限公司 | A method of preparing acetone using synthesis triacetonamine process byproduct |
| CN111285794A (en) * | 2018-12-07 | 2020-06-16 | 赢创运营有限公司 | Improved process for the preparation of triacetonamine |
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| CN103663773A (en) * | 2012-09-07 | 2014-03-26 | 赢创工业集团股份有限公司 | Treatment method of wastewater flows generated in treatment of triacetonamine-containing reaction mixture |
| CN108383704A (en) * | 2018-05-01 | 2018-08-10 | 衡水凯亚化工有限公司 | A method of preparing acetone using synthesis triacetonamine process byproduct |
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