CN101507917B - Solid base catalyst for synthesizing alkanolamide type compound and preparation method thereof - Google Patents
Solid base catalyst for synthesizing alkanolamide type compound and preparation method thereof Download PDFInfo
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- CN101507917B CN101507917B CN2009100813345A CN200910081334A CN101507917B CN 101507917 B CN101507917 B CN 101507917B CN 2009100813345 A CN2009100813345 A CN 2009100813345A CN 200910081334 A CN200910081334 A CN 200910081334A CN 101507917 B CN101507917 B CN 101507917B
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- magnesia
- solid base
- base catalyst
- alumina hydrotalcite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000007787 solid Substances 0.000 title claims abstract description 29
- 150000001875 compounds Chemical class 0.000 title abstract description 14
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 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 abstract description 34
- 229960001545 hydrotalcite Drugs 0.000 claims abstract description 34
- 229910001701 hydrotalcite Inorganic materials 0.000 claims abstract description 34
- 239000002243 precursor Substances 0.000 claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 26
- 239000002585 base Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000003513 alkali Substances 0.000 claims description 18
- 238000002425 crystallisation Methods 0.000 claims description 18
- 230000008025 crystallization Effects 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 15
- 239000004202 carbamide Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 13
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000002955 isolation Methods 0.000 claims description 11
- 238000010899 nucleation Methods 0.000 claims description 11
- 230000006911 nucleation Effects 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000012266 salt solution Substances 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229910018134 Al-Mg Inorganic materials 0.000 claims description 8
- 229910018467 Al—Mg Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229940072033 potash Drugs 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims 1
- 229910001051 Magnalium Inorganic materials 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 239000004902 Softening Agent Substances 0.000 abstract description 3
- 239000013556 antirust agent Substances 0.000 abstract description 3
- 239000002562 thickening agent Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- 239000000271 synthetic detergent Substances 0.000 abstract description 2
- 239000002216 antistatic agent Substances 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000003599 detergent Substances 0.000 abstract 1
- 239000004872 foam stabilizing agent Substances 0.000 abstract 1
- 238000009472 formulation Methods 0.000 abstract 1
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N Methyl stearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 10
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000007791 liquid phase Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 230000036571 hydration Effects 0.000 description 6
- 238000006703 hydration reaction Methods 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- GHJOEPMHSNXADF-UHFFFAOYSA-N 1-aminoicosan-2-ol Chemical compound CCCCCCCCCCCCCCCCCCC(O)CN GHJOEPMHSNXADF-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000009938 salting Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- -1 aldehyde ketone Chemical class 0.000 description 2
- 238000011938 amidation process Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- HSQFVBWFPBKHEB-UHFFFAOYSA-N 2,3,4-trichlorophenol Chemical compound OC1=CC=C(Cl)C(Cl)=C1Cl HSQFVBWFPBKHEB-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 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 description 1
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 1
- 229910020068 MgAl Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003225 biodiesel Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- VTVVPPOHYJJIJR-UHFFFAOYSA-N carbon dioxide;hydrate Chemical compound O.O=C=O VTVVPPOHYJJIJR-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 239000007785 strong electrolyte Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229950002929 trinitrophenol Drugs 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/10—Magnesium; Oxides or hydroxides thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/16—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms
- C07C233/17—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom
- C07C233/18—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having the nitrogen atom of at least one of the carboxamide groups bound to a carbon atom of a hydrocarbon radical substituted by singly-bound oxygen atoms with the substituted hydrocarbon radical bound to the nitrogen atom of the carboxamide group by an acyclic carbon atom having the carbon atom of the carboxamide group bound to a hydrogen atom or to a carbon atom of an acyclic saturated carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Catalysts (AREA)
Abstract
The invention relates to a solid base catalyst for synthesizing alkanolamide compounds and a preparation method thereof, and belongs to the technical field of solid base catalyst. Magnalium hydrotalcite is taken as a precursor of the catalyst and used to prepare the solid base catalyst through calcination and rehydration, and the formulation of the magnalium hydrotalcite solid base catalyst is Mg1-xAlx(OH)2<x+>(OH-)x.mH2O. The alkanolamide compounds are reaction products, have good surface activity, are one of the most important varieties of non-ionic surface active agents, are important active monomers of a modern synthetic detergent, and are widely applied to detergents, foam stabilizers, thickeners, softening agents, anti-rust agents, antistatic agents, and the like.
Description
Technical field
The invention belongs to the solid base catalyst technical field, particularly relate to a kind of synthetic alkanolamide compounds solid base catalyst of catalysis and preparation method of being used for.
Background technology
Biodiesel claims fatty acid methyl ester again, is a kind of novel biomass fuel, is the fossil fuel substitute of high-quality, and the performance that it is superior to the friendly and the recyclability thereof of environment, has obtained paying attention to.But, its expensive industrialization process that hinders biomass fuel.Chemical products by the production high added value increase the hot issue that profit is present research.With the natural acid is the grease derivative that raw material is made, and then synthetic alkanolamide compounds.Not only can turn waste into wealth, and the products obtained therefrom excellent performance, biological degradability is good, pollution is little, safety in utilization is good.
Alkanolamide is a kind of new non-ionic surfactants, faint yellow solid, nontoxic nonirritant.Have amido link in its molecule, do not dissociate in the aqueous solution, its hydrophilic group mainly is to be made of some hydroxyls.These characteristics have determined non-ionic surface active agent in some aspects than ionic surfactant superior performance just.Because be not ionic condition in solution, so good stability, be not subject to strong electrolyte and have influence, be not subject to the influence of soda acid yet, good with other type activating agent intermiscibility, can easier mix use,, in water and in the organic solvent, different solvabilities be arranged all along with the variation of structure, there be not cloud point with the difference of other surfactant with it, performances such as good thickening, steady bubble, foam enhancing, decontamination, calcium soap dispersion, emulsification are arranged, be widely used in washing agent, foam stabiliser, thickener, softening agent, antirust agent, antistatic additive etc.
Adopt fatty acid methyl ester and MEA to carry out amidation process in the traditional handicraft and produce the alkanolamide compounds.Reaction catalyst commonly used mainly is a liquid alkali catalyst, such as potash, sodium carbonate, potassium hydroxide, NaOH, sodium methoxide, caustic alcohol etc.Wherein catalyst selectivitys such as potash, sodium carbonate, potassium hydroxide, NaOH are relatively poor, are difficult for reclaiming, and severe corrosion equipment causes very big pollution to environment; Though and catalyst such as sodium methoxide, caustic alcohol make the product purity height, accessory substance is few, and its cost is higher and stable bad.Sodium chemistry character is very active, and transportation is preserved inconvenient; Sodium methoxide is to oxygen sensitive, and is inflammable, is dissolved in methyl alcohol, ethanol, meets water and resolves into methyl alcohol and NaOH, decomposes in the air more than 126.6 ℃.As everyone knows, compare with liquid alkali catalyst, solid base catalyst have not etching apparatus, environmental pollution little, be easy to advantages such as recovery.
Houghite is a class layered inorganic functional material, have the adjustable of laminate chemical composition, structural advantages such as interlayer ion kind and adjustable number, be widely used as catalyst, release agent, ion-exchange and adsorbent etc., can be used as the adsorbent of hydrophobic compound with the LDHs of Al and Li and straight-chain acid formation.[J.Phys.Chem., 1989,93:376-382]; Utilize selectivity and the different insertion ability of isomers of LDHs to come separating isomerism body [J.Am.Chem.Soc., 1984,106:5772-5779]; From waste water, adsorb trichlorophenol, 2,4,6,-T, trinitrophenol or the like [Appl.Clay Sci., 1995,10:131-145].The solid base catalyst that particularly with the hydrotalcite is the presoma preparation has demonstrated catalytic performance preferably in multiple catalytic reaction, people such as Zoltan with Mg/Al than being 3 MgAl-LDHs base catalyst [J.Mol.Catal.A:Chemical as intramolecular cyclization reaction and intermolecular cyclization reaction, 2000,161:149-155].People such as Rousselot are used for the Knoevenagel condensation reaction with Mg-Ga-Al-LDHs as base catalyst, have very high reactivity [Int.J.Inorg.Mater., 1999,1:165-174].People such as Reichle study different aldehyde ketone condensation reactions on MgAl (O) composite oxides, point out that this class base catalyst has the high life than the heterogeneous catalyst that other is used for the aldehyde ketone condensation reaction, high stability, high selectivity and stronger advantages such as reproducibility [J.Catal., 1980,63:295-306].And being applied to synthetic alkanolamide compounds as solid base catalyst, houghite also do not have pertinent literature or application report at present.
Summary of the invention
The object of the present invention is to provide a kind of solid base catalyst for synthesizing alkanolamide type compound and preparation method, have active height, applied widely, prepare characteristics such as simple, with low cost.
The preparation method of solid base catalyst provided by the invention at first utilizes common houghite preparation methods such as nucleation/crystallization isolation method and urea method to prepare particle diameter to be nanoscale or micron-sized magnesia-alumina hydrotalcite precursor, then with the roasting and rehydrated of precursor process, obtain this solid base catalyst, be used for the synthetic alkanolamide compounds of catalysis.
The synthetic alkanolamide compounds solid base catalyst of catalysis that is used for provided by the invention, its chemical general formula is:
[Mg
1-xAl
x(OH)
2]
x+(OH
-)
x·mH
2O
Wherein, the span of x is (0.2＜x＜0.33); M is the quantity (0.1＜m＜10) of the crystallization water.
The concrete preparation process of magnesia-alumina hydrotalcite solid base catalyst provided by the invention is as follows:
At first utilize common houghite preparation methods, prepare magnesia-alumina hydrotalcite precursor as nucleation/crystallization isolation method and urea method, with the roasting and rehydrated of precursor process, obtain this solid base catalyst, carrying out the XRD sign then, and be used for the synthetic alkanolamide compounds of catalysis, utilize the productive rate and the selectivity of liquid-phase chromatographic analysis reaction.
1. prepare magnesia-alumina hydrotalcite precursor, its chemical general formula is:
[Mg
1-xAl
x(OH)
2]
x+(CO
3 2-)
x/2·nH
2O
Wherein, the span of x is (0.2＜x＜0.33); N is the quantity (0.1＜n＜10) of the crystallization water.
The mixing salt solution of A preparation divalence solubility magnesium salts and trivalent aluminum soluble salt, wherein bivalent metal ion concentration is 0.12-12mol/L, divalence, trivalent metal ion mol ratio are 2-4 times;
Described divalence magnesium soluble-salt is a kind of of nitrate, sulfate, acetate or chlorate, is preferably magnesium nitrate; Described trivalent aluminium soluble-salt is a kind of in nitrate, sulfate, acetate or the chlorate, is preferably aluminum nitrate;
The mixed-alkali solution of B preparation alkali and soluble inorganic salt, wherein the concentration of alkali is 0.096-9.6mol/L, the mol ratio of alkali and inorganic potassium (or sodium) salt is 2.4-3.2 times;
Described alkali is NaOH, and potassium hydroxide a kind of is preferably NaOH; Described inorganic salts are sodium carbonate, and a kind of in the potash is preferably sodium carbonate;
The urea liquid of C preparation 0.1-5mol/L;
When D nucleation crystallization isolation method prepares catalyst, it is characterized in that: with the mixing salt solution of steps A preparation and the mixed-alkali solution of step B preparation, be added in the colloid mill at 5-70 ℃ and drip, back-mixing number minute, move in the there-necked flask then, reacted 4-100 hour down at 10 ℃-100 ℃, get magnesia-alumina hydrotalcite precursor slurry;
When the E urea method prepares catalyst, it is characterized in that:, after evenly mixing, move in the band teflon-lined stainless steel cauldron the mixing salt solution of steps A preparation and the urea liquid of step C preparation, 10 ℃-110 ℃ reactions 4-100 hour, get magnesia-alumina hydrotalcite precursor slurry;
The slurries of F nucleation crystallization isolation method or the resulting magnesia-alumina hydrotalcite of urea method precursor for several times to pH to 7-8, behind dry 24h under 10-120 ℃, promptly get magnesia-alumina hydrotalcite precursor through centrifuge washing.
2. the preparation of Al-Mg composite metal oxide
The magnesia-alumina hydrotalcite precursor of nucleation crystallization isolation method or urea method preparation is put into the atmosphere kiln roasting of nitrogen protection; heating rate is 1-50 ℃/min; rise to 100-1000 ℃ by room temperature; roasting time is 1-50 hour; after roasting is finished; naturally be cooled to room temperature, product of roasting is an Al-Mg composite metal oxide.
3. the preparation of magnesia-alumina hydrotalcite solid base catalyst
With step 2 gained Al-Mg composite metal oxide, put into CO
2Carry out rehydrated when the hydration of gram Al-Mg composite metal oxide (every need remove the volume of CO2 water be 20-200ml) in the water; adopt nitrogen protection; the rehydrated time is 1-50 hour; reaction finishes; product is carried out quick pumping rate; in 10-80 ℃ of following vacuum drying chamber dry 5-48 hour, the material that obtains was the magnesia-alumina hydrotalcite solid base catalyst.
But the amidation process of solid base catalyst catalysis ester class of the present invention and monoethanolamine, its chemical equation is:
RCOOR
1+H
2NC
2H
4OH→RCONHC
2H
4OH+HOR
1，
Wherein, R is the alkane with different carbon atom numbers with R1, and the carbon atom number of R is 12～18, R
1The carbon atom number be 1～10.
The invention has the advantages that, product is the alkanolamide compounds, has the surface of good activity, being one of most important kind in the non-ionic surface active agent, is activated monomer important in the modern synthetic detergent, is widely used in washing agent, foam stabiliser, thickener, softening agent, antirust agent and antistatic additive etc.
Description of drawings
Fig. 1 is that the magnalium of nucleation/crystallization isolation method preparation is than being 2/1 the hydrotalcite (b) and the XRD figure of rehydrated product (a) thereof;
Fig. 2 is that the magnalium of nucleation/crystallization isolation method preparation is than being 3/1 the hydrotalcite (b) and the XRD figure of rehydrated product (a) thereof;
Fig. 3 is that the magnalium of nucleation/crystallization isolation method preparation is than being 4/1 the hydrotalcite (b) and the XRD figure of rehydrated product (a) thereof;
Fig. 4 for the magnalium of urea method preparation than being 2/1 the hydrotalcite (b) and the XRD figure of rehydrated product (a) thereof.
The specific embodiment
Embodiment 1
With the magnesium nitrate of deionized water preparation 250ml and the mixing water salting liquid of aluminum nitrate, wherein, the concentration of magnesium is 0.8mol/L, and the concentration of aluminium is 0.4mol/L; Other prepares the NaOH of 250ml and the mixed ammonium/alkali solutions of sodium carbonate, and wherein, concentration sodium hydroxide is 1.9 mol, and the concentration of sodium carbonate is 0.8 mol.Behind mixing salt solution and the ultrasonic 10min of aqueous slkali, to react in above-mentioned two kinds of mixed solutions immigration colloid mill, voltage 140V, 4500rpm, reaction time is 2-3min, after reaction finishes, slurries are moved in the 1000ml there-necked flask 95 ℃ of following backflow crystallization 5 hours, use the deionized water centrifuge washing between the pH value scope 7-8 in the gained slurries, at 100 ℃ of dry 24h, grind then, place atmosphere furnace again in 500 ℃ of roastings 15 hours, put into carbon dioxide water hydration 8 hours again, 40 ℃ of following vacuum drying are 24 hours then, promptly prepare the magnesia-alumina hydrotalcite solid base catalyst, and its chemical composition is [Mg
2Al (OH)
6] (OH
-) 2H
2O.
Get methyl stearate 14.925g, MEA 3.36g, catalyst 0.915g, put into the 100ml there-necked flask, reaction is after 4 hours in 140 ℃ of oil baths, and liquid phase efficient liquid phase chromatographic analysis, the conversion ratio 92.2% of methyl stearate are carried out in sampling, the selectivity of stearyl monoethanolamine is 77.7%, and productive rate is 71.6%.
Embodiment 2
In 100ml polytetrafluoroethylcontainer container or glass container, with Mg (NO
3) 2.6H
2O and Al (NO
3) 3.9H
2O is dissolved in the 75ml deionized water by 2: 1 mol ratios, is mixed with the solution that total concentration is 0.3M.Ratio in urea/NO3-=4.0 adds urea and makes it dissolving, and airtight container was in 90 ℃ of following isothermal reactions 3 days, after treating the solution cooling, filter and wash the white precipitate of gained, dry 24h under 100 ℃ promptly gets magnalium carbonate hydrotalcite, grind, place atmosphere furnace in 500 ℃ of roastings 15 hours again, put into carbon dioxide water hydration 8 hours again, 40 ℃ of following vacuum drying are 24 hours then, promptly make the magnesia-alumina hydrotalcite solid base catalyst, its chemical composition is [Mg
2Al (OH)
6] (OH
-) 2H
2O.
Get methyl stearate 14.925g, MEA 3.36g, catalyst 0.915g, put into the 100ml there-necked flask, reaction is after 4 hours in 140 ℃ of oil baths, and liquid phase analysis is carried out in sampling, the conversion ratio 89.4% of methyl stearate, the selectivity of stearyl monoethanolamine are 98.2%, and productive rate is 87.8%.
Embodiment 3
With the magnesium nitrate of deionized water preparation 250ml and the mixing water salting liquid of aluminum nitrate, wherein, the concentration of magnesium is 1.2mol/L, and the concentration of aluminium is 0.4mol/L; Other prepares the NaOH of 250ml and the mixed ammonium/alkali solutions of sodium carbonate, and wherein, I am 2.56mol/L for a concentration sodium hydroxide, and the concentration of sodium carbonate is 0.8mol/L.Behind mixing salt solution and the ultrasonic 10min of aqueous slkali, to react in above-mentioned two kinds of mixed solutions immigration colloid mill, voltage 140V, 4500rpm, reaction time is 2-3min, after reaction finishes, slurries are moved in the 1000ml there-necked flask, 95 ℃ of following backflow crystallization 5 hours, with the gained slurries with the deionized water centrifuge washing between the pH value scope 7-8, then at 100 ℃ of dry 24h, grind, place atmosphere furnace again, put into carbon dioxide water hydration 8 hours again in 500 ℃ of roastings 15 hours, 40 ℃ of following vacuum drying are 24 hours then, promptly prepare the magnesia-alumina hydrotalcite solid base catalyst.
Get methyl stearate 14.925g, MEA 3.36g, catalyst 0.915g, put into the 100ml there-necked flask, reaction is after 4 hours in 140 ℃ of oil baths, and liquid phase analysis is carried out in sampling, the conversion ratio 96.3% of methyl stearate, the selectivity of stearyl monoethanolamine are 95.4%, and productive rate is 91.9%.
Embodiment 4
With the magnesium nitrate of deionized water preparation 250ml and the mixing water salting liquid of aluminum nitrate, wherein, the concentration of magnesium is 0.8mol/L, and the concentration of aluminium is 0.2mol/L; Other prepares the NaOH of 250ml and the mixed ammonium/alkali solutions of sodium carbonate, and wherein, I am 1.6mol/L for a concentration sodium hydroxide, and the concentration of sodium carbonate is 0.4mol/L.Behind mixing salt solution and the ultrasonic 10min of aqueous slkali, to react in above-mentioned two kinds of mixed solutions immigration colloid mill, voltage 140V, 4500rpm, reaction time is 2-3min, after reaction finishes, slurries are moved in the 1000ml there-necked flask, 95 ℃ of following backflow crystallization 5 hours, with the gained slurries with the deionized water centrifuge washing between the pH value scope 7-8, then at 100 ℃ of dry 24h, grind, place atmosphere furnace again, put into carbon dioxide water hydration 8 hours again in 500 ℃ of roastings 15 hours, 40 ℃ of following vacuum drying are 24 hours then, promptly prepare the magnesia-alumina hydrotalcite solid base catalyst.
Get methyl stearate 14.925g.MEA 3.36g, catalyst 0.915g puts into the 100ml there-necked flask, and reaction is after 4 hours in 140 ℃ of oil baths, and liquid phase analysis is carried out in sampling, the conversion ratio 95.0% of methyl stearate, the selectivity of stearyl monoethanolamine is 66.2%, productive rate is 62.9%.
Embodiment 5
With the magnesium nitrate of deionized water preparation 250ml and the mixing water salting liquid of aluminum nitrate, wherein, the concentration of magnesium is 0.8mol/L, and the concentration of aluminium is 0.4mol/L; Other prepares the NaOH of 250ml and the mixed ammonium/alkali solutions of sodium carbonate, and wherein, I am 1.9mol/L for a concentration sodium hydroxide, and the concentration of sodium carbonate is 0.8mol/L.Behind mixing salt solution and the ultrasonic 10min of aqueous slkali, to react in above-mentioned two kinds of mixed solutions immigration colloid mill, voltage 140V, 4500rpm, reaction time is 2-3min, after reaction finishes, slurries are moved in the 1000ml there-necked flask, 95 ℃ of following backflow crystallization 5 hours, with the gained slurries with the deionized water centrifuge washing between the pH value scope 7-8, then at 100 ℃ of dry 24h, grind, place atmosphere furnace again, put into carbon dioxide water hydration 8 hours again in 500 ℃ of roastings 15 hours, 40 ℃ of following vacuum drying are 24 hours then, promptly prepare the magnesia-alumina hydrotalcite solid base catalyst.
Get methyl stearate 14.925g, MEA 3.36g, catalyst 0.915g, put into the 100ml there-necked flask, reaction is after 4 hours in 140 ℃ of oil baths, and liquid phase analysis is carried out in sampling, the conversion ratio 87.1% of methyl stearate, the selectivity of stearyl monoethanolamine are 67.1%, and productive rate is 58.4%.
Claims (1)
1. an alkanolamide synthesizes the preparation method who uses solid base catalyst, it is characterized in that: may further comprise the steps:
(1) preparation magnesia-alumina hydrotalcite precursor;
(2) preparation of Al-Mg composite metal oxide
The magnesia-alumina hydrotalcite precursor of nucleation crystallization isolation method or urea method preparation is put into the atmosphere kiln roasting of nitrogen protection, heating rate is 1-50 ℃/min, rise to 100-1000 ℃ by room temperature, roasting time is 1-50 hour, after roasting is finished, naturally be cooled to room temperature, product of roasting is an Al-Mg composite metal oxide;
(3) preparation of magnesia-alumina hydrotalcite solid base catalyst
With step (2) gained Al-Mg composite metal oxide, put into CO
2Carry out rehydratedly in the water, adopting nitrogen protection, rehydrated time is 1-50 hour, and reaction finishes, and product is carried out quick suction filtration, and in 10-80 ℃ of following vacuum drying chamber dry 5-48 hour, the material that obtains was the magnesia-alumina hydrotalcite solid base catalyst; When rehydrated, every gram Al-Mg composite metal oxide need remove CO
2The volume of water is 20-200ml;
The preparation process of described preparation magnesia-alumina hydrotalcite precursor is:
The mixing salt solution of A preparation divalence solubility magnesium salts and trivalent aluminum soluble salt, wherein bivalent metal ion concentration is 0.12-12mol/L, divalence, trivalent metal ion mol ratio are 2-4;
Described divalence magnesium soluble-salt is a kind of of nitrate, sulfate, acetate or chlorate;
Described trivalent aluminium soluble-salt is a kind of in nitrate, sulfate, acetate or the chlorate;
The mixed-alkali solution of B preparation alkali and soluble inorganic salt, wherein the concentration of alkali is 0.096-9.6mol/L, the mol ratio of alkali and inorganic salts is 2.4-3.2;
Described alkali is NaOH, potassium hydroxide a kind of; Described inorganic salts are sodium carbonate, a kind of in the potash;
The urea liquid of C preparation 0.1-5mol/L;
When D nucleation crystallization isolation method prepares catalyst, with the mixing salt solution of steps A preparation and the mixed-alkali solution of step B preparation, be added in the colloid mill at 5-70 ℃ and drip, back-mixing number minute, move in the there-necked flask then, reacted 4-100 hour down at 10 ℃-100 ℃, get the slurries of magnesia-alumina hydrotalcite precursor;
When urea method prepares catalyst, with the mixing salt solution of steps A preparation and the urea liquid of step C preparation, after evenly mixing, move in the band teflon-lined stainless steel cauldron, 10 ℃-110 ℃ reactions 4-100 hour, get the slurries of magnesia-alumina hydrotalcite precursor;
The slurries of E nucleation crystallization isolation method or the resulting magnesia-alumina hydrotalcite of urea method precursor for several times to pH to 7-8, behind dry 24h under 10-120 ℃, get magnesia-alumina hydrotalcite precursor through centrifuge washing;
The chemical general formula of described magnesia-alumina hydrotalcite precursor is: [Mg
1-xAl
x(OH)
2]
X+(CO
3 2-)
X/2NH
2O, wherein, the span of x is 0.2＜x＜0.33; N is the quantity of the crystallization water, 0.1＜n＜10.
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| PCT/CN2009/072508 WO2010111849A1 (en) | 2009-04-02 | 2009-06-29 | Solid basic catalyst for synthesizing alkanolamide compounds and preparation method thereof |
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| CN102140379A (en) * | 2011-02-25 | 2011-08-03 | 常州大学 | Method for preparing nitrogen phosphate-containing extreme pressure abrasion-resistant lubricating additive by using biodiesel |
| CN102964195B (en) * | 2012-11-28 | 2015-06-24 | 温州大学 | Method for preparing second-level and third-level substituted amide |
| CN103242189B (en) * | 2013-05-17 | 2014-06-18 | 杨雪飞 | Method for catalytic preparation of aromatic amide compound by solid alkali |
| CN105601150B (en) * | 2015-12-17 | 2017-10-27 | 江苏苏博特新材料股份有限公司 | A kind of reinforcing steel bar corrosion inhibitor and its application |
| CN109420482A (en) * | 2017-09-05 | 2019-03-05 | 张家港市沐和新材料技术开发有限公司 | A kind of magnesia-alumina composite catalyst and preparation method thereof |
| EP3743494A1 (en) | 2018-01-26 | 2020-12-02 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a binder and optional carrier |
| US11377628B2 (en) | 2018-01-26 | 2022-07-05 | Ecolab Usa Inc. | Solidifying liquid anionic surfactants |
| CA3089629A1 (en) | 2018-01-26 | 2019-08-01 | Ecolab Usa Inc. | Solidifying liquid amine oxide, betaine, and/or sultaine surfactants with a carrier |
| CN109289828A (en) * | 2018-11-18 | 2019-02-01 | 邵阳天堂助剂化工有限公司 | A method of roasting state hydrocalumite catalyzed synthesis of fatty acid methyl esters |
| CN110624529A (en) * | 2019-09-26 | 2019-12-31 | 中国天辰工程有限公司 | Preparation and use methods of hydroxide intercalation calcium magnesium aluminum hydrotalcite solid base catalyst |
| CN111111654A (en) * | 2019-12-31 | 2020-05-08 | 湘潭大学 | Preparation method and application of improved Pt/Mg-Al-O dehydrogenation catalyst |
| CN115197097A (en) * | 2021-04-08 | 2022-10-18 | 烟台东方化学有限公司 | Preparation method of safe bacteriostatic octanoyl hydroximic acid |
| CN114534731B (en) * | 2022-01-25 | 2023-10-31 | 晋中学院 | Preparation method and application of hydrotalcite-based carbon doped copper-magnesium-aluminum composite oxide catalyst |
| CN115041129B (en) * | 2022-06-29 | 2023-10-31 | 润和科华催化剂(上海)有限公司 | Dechlorination agent for removing chloride in olefin-containing process and preparation method thereof |
| CN115475613A (en) * | 2022-09-29 | 2022-12-16 | 北部湾大学 | Modified oyster shell solid base catalyst for synthesizing biodiesel and preparation method thereof |
| CN116081671B (en) * | 2023-01-17 | 2024-09-17 | 广东华特气体股份有限公司 | Porous double-metal hydroxide and preparation method and application thereof |
| CN117229461B (en) * | 2023-11-10 | 2024-02-02 | 山东永创材料科技有限公司 | Preparation method and application of furfuryl ketone resin |
| CN117563586A (en) * | 2023-11-24 | 2024-02-20 | 山东长泽新材料科技有限公司 | Solid catalyst and method for efficiently synthesizing methacrolein |
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| CN1467177A (en) * | 2002-06-24 | 2004-01-14 | 北京化工大学 | Method for assembling anion type supramolecular intercalation structure material |
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