CN101596452B - Catalyst for preparing dimethyl carbonate by urea alcoholysis and preparation method thereof - Google Patents
Catalyst for preparing dimethyl carbonate by urea alcoholysis and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 236
- 238000002360 preparation method Methods 0.000 title claims abstract description 69
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000004202 carbamide Substances 0.000 title claims abstract description 14
- 238000006136 alcoholysis reaction Methods 0.000 title claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 229910052596 spinel Inorganic materials 0.000 claims abstract description 7
- 239000011029 spinel Substances 0.000 claims abstract description 7
- 238000009826 distribution Methods 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims description 61
- 230000000694 effects Effects 0.000 claims description 52
- 238000000034 method Methods 0.000 claims description 47
- 238000001035 drying Methods 0.000 claims description 36
- 239000000470 constituent Substances 0.000 claims description 35
- 238000007598 dipping method Methods 0.000 claims description 21
- 206010013786 Dry skin Diseases 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 20
- 230000001105 regulatory effect Effects 0.000 claims description 20
- 238000002803 maceration Methods 0.000 claims description 14
- 239000000284 extract Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 5
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 239000002280 amphoteric surfactant Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000002815 homogeneous catalyst Substances 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000003321 amplification Effects 0.000 abstract 1
- 239000003622 immobilized catalyst Substances 0.000 abstract 1
- 238000003199 nucleic acid amplification method Methods 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 65
- 239000011701 zinc Substances 0.000 description 47
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 42
- 238000001354 calcination Methods 0.000 description 24
- 239000011787 zinc oxide Substances 0.000 description 21
- 239000011133 lead Substances 0.000 description 18
- 238000010792 warming Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000005470 impregnation Methods 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 238000006424 Flood reaction Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 8
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 5
- 229910000464 lead oxide Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 102220470372 Thymosin beta-10_K12A_mutation Human genes 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001676 gahnite Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000005832 oxidative carbonylation reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HZTBQULISMUXEL-UHFFFAOYSA-N dimethyl carbonate;methanol;hydrate Chemical compound O.OC.COC(=O)OC HZTBQULISMUXEL-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YEYZNBKNDWPFSQ-UHFFFAOYSA-N methanol;urea Chemical compound OC.NC(N)=O YEYZNBKNDWPFSQ-UHFFFAOYSA-N 0.000 description 1
- 125000005525 methide group Chemical group 0.000 description 1
- -1 methoxyl group compound Chemical class 0.000 description 1
- 238000006198 methoxylation reaction Methods 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010530 solution phase reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalyst for preparing dimethyl carbonate by urea alcoholysis and a preparation method thereof, wherein the specific surface area of the catalyst is 150-350 m2A specific pore volume of 0.5 to 2.0 cm/g3A pore size distribution of 50 to 150
The carrier is gamma-Al2O3The catalyst accounts for 50-80 wt% of the whole catalyst, and the balance is active components; the main active component is at least one of ZnO, CaO and PbO, the oxide of the active component and the carrier alumina can form a stable spinel structure, the stability of the catalyst is good, and the stable operation life of the catalyst can reach more than 500 hours. The catalyst has higher catalytic activity for synthesizing dimethyl carbonate by the liquid phase reaction of urea and methanol, the preparation method of the catalyst is simple, the load can be completed without special equipment, and the industrial amplification is facilitated. The catalyst is an immobilized catalyst, and the problem that the existing homogeneous catalyst is difficult to recover is solved.
Description
Technical field
The present invention relates to a kind of catalyst for preparing dimethyl carbonate by using urea alcoholysis and preparation method thereof, particularly a kind of load metal oxide Catalysts and its preparation method that is used for urea and methyl alcohol reaction production dimethyl carbonate.
Background technology
Dimethyl carbonate is a kind of have multiple reactivity, eco-friendly organic chemicals, reactions such as alternative hypertoxic phosgene, dimethyl suflfate etc. carry out carbonylation, methylate, methoxylation, have active reaction property, be subject to people's attention day by day in recent years.At present, ripe dimethyl carbonate synthetic method mainly contains phosgenation, oxidative carbonylation method and ester-interchange method.But the phosgenation complex process, raw material severe toxicity, accessory substance HCl severe corrosion equipment; Liquid-phase oxidative carbonylation method water byproduct has a strong impact on catalyst activity, and chloride catalyst corrosivity is strong, the weak point of receiving a mandate, and uses the nitrogen-containing oxide severe corrosion equipment in the vapor phase method reaction, and the product separation difficulty, the catalyst costliness of using; Ester-interchange method reaction raw materials oxirane is dangerous big, and the molecular balance conversion ratio is low, product separation and purification difficulty.These drawbacks limit the suitability for industrialized production and the popularization of above-mentioned several method.Dimethyl carbonate preparation method newly developed in recent years mainly contains carbon dioxide-methyl alcohol direct synthesis technique and urea-methyl alcohol direct synthesis technique.Carbon dioxide-methyl alcohol method mainly adopts organo-metallic compound to make catalyst, costs an arm and a leg, reaction conversion ratio is low and catalyst separation is difficult, and exploitation cheapness, high activity, heterogeneous catalysis are the main directions of studying at present.
Urea-methyl alcohol method is because its raw material is cheap and easy to get, technology is simple, reaction condition is gentle, and avoided the separation difficult problem of dimethyl carbonate-water-methanol complex system and become the focus of domestic and international research.The catalyst that is used for urea-methyl alcohol method Synthesis of dimethyl carbonate at present mainly contains organo-tin compound and alkali metal compound.
WO95-17369 has reported with organo-tin compounds such as Dibutyltin oxide, dibutyl stannous methides and has made catalyst that the mode that steams product with urea-methyl alcohol reaction is simultaneously continuously produced dimethyl carbonate, obtains higher product yield.WO0012212 has reported with organo-tin compound and has made catalyst that higher boiling electron donor chemical combination is made co-catalyst and solvent, adopts the method that steams product continuously to produce dimethyl carbonate, obtains higher conversion ratio and product yield.Though organo-tin compound has catalytic activity and product yield preferably because this compounds severe toxicity, cost an arm and a leg, homogeneous catalyst reclaims difficulty, influence use from product.
It is that in the oxide of main body and lithium, magnesium, nickel, lead, aluminium, iron, molybdenum, zirconium, lanthanum 1～2 kind is formed mixed catalyst that CN1416949A has reported by zinc oxide, at urea: under methyl alcohol=1: 20～40 conditions, adopt the ZnO-La of coprecipitation preparation
2O
3Under the binary catalyst effect, the dimethyl carbonate yield reaches 49.7%, yet catalyst is a nano-scale particle, has the problem of separating with product, is unfavorable for industrial applications.US5534649 has reported hydroxide, carbonate and the methoxyl group compound as catalyst that adopts metals such as Rb, Cs, K, employing is continuously removed the explained hereafter dimethyl carbonate of ammonia, but this poor catalyst activity, the dimethyl carbonate yield is very low, and successive reaction is accumulated conversion ratio and had only 18.5% after 140 hours.Chinese patent CN1597096A discloses a kind of loaded catalyst that is used for urea methyl alcohol method Synthesis of dimethyl carbonate, and catalyst consists of active component 20～50wt%, carrier 80～50wt%.Adopt special catalytic distillation device to carry out evaluating catalyst, the highest yield reaches 76.8%.Since directly adopt one step of equal-volume infusion process, the active component skewness, a large amount of active components do not have and carrier forms stable crystal structure, and therefore, active component runs off easily in the use, and the stability and the life-span of catalyst are bad.
In sum, efficient, the environmental protection of exploitation, the simple solid catalyst of preparation are urea-industrialized key points of methyl alcohol method process for synthesizing methyl carbonate.
Adding surfactant in Preparation of Catalyst is a kind of method of using always, and Chinese patent CN1559681 adopts the method for adding surfactant to regulate the size and the hydrauture of catalyst activity component manganese dioxide crystal grain, has significantly improved catalyst activity.CN1528520 has announced a kind of solid catalyst preparation method who adds surfactant, non-ionic surface active agent, organic solvent and the aqueous solution that contains catalyst activity component are mixed with the microemulsion of w/o type, under stirring condition, in the microemulsion that is made into, add catalyst carrier and solid precipitating reagent formation sediment, sediment obtains loaded catalyst through washing, roasting, the catalyst that makes has the advantage that the active component particle diameter is little, reactivity is high, the preparation method is simple to operation, and this method is applicable to the various loaded catalysts of preparation.CN1453072, CN1453073 when making loaded catalyst, add the surfactant rear catalyst once on amount many, coating is difficult for be full of cracks and peels off, last amount is lost little.JP62132548A adds surfactant when the preparation loaded catalyst can improve active component decentralization and specific surface area of catalyst, thereby has improved activity of such catalysts.In preparation dimethyl carbonate catalyst process, also can adopt suchlike method to improve the performance of catalyst.
Summary of the invention
The invention provides a kind of catalyst for preparing dimethyl carbonate by using urea alcoholysis and preparation method thereof, particularly a kind of high capacity type alkali metal oxide Catalysts and its preparation method.
Being characterized as of catalyst of the present invention: carrier is γ-Al
2O
3, accounting for 50～80wt% of whole catalyst, all the other are active component; Main active component is at least a among ZnO, CaO, the PbO, and preferred ZnO, PbO account for 80～100wt% of gross activity component; Also can contain in the catalyst activity component and help component, be La
2O
3, MgO, Cr
2O
3, ZrO, MnO
2, SnO
2, CuO etc., can be wherein one or more, preferred La
2O
3, SnO
2, content accounts for 0～20wt% of gross activity component; The specific area of catalyst is 150～350m
2/ g, specific pore volume are 0.5～2.0cm
3/ L, pore-size distribution are 50～150
Catalyst granules accounts for 65～80% of surface active composition content apart from center 1/3R place active component content, account for 80～90% of surface active composition content apart from center 2/3R place active component content, R is the distance of catalyst granules center to catalyst surface among the present invention; Preferably catalyst granules center active component content accounts for 50～65% of surface active composition content, catalyst of the present invention, main active component and Al
2O
3Be preferably formed as the stable spinel structure.The catalyst activity constituent content distributes and adopts electronic microscope photos, and the sampled point radius is 50～70 μ m.
It is 80～350m that catalyst carrier is used specific area
2/ g, specific pore volume are 0.5～2.0cm
3/ L, pore-size distribution are 50～150
γ-Al
2O
3, carrier can be prepared into various shape, can realize that the present invention is not particularly limited fully in the prior art.Can adopt commercially available γ type Al
2O
3Carrier, also can use boehmite be formed into earlier difformity again roasting become γ-Al
2O
3Carrier.This process also has been unusual mature technique, and the present invention is not repeated.
The present invention also provides a kind of this Preparation of catalysts method: get the soluble-salt preparation maceration extract of active component oxide, regulating pH is 1.0～5.0; Add anion, nonionic or the amphoteric surfactant of 0.01～0.1ml/l in the maceration extract, and mix; Adopt two steps or multistep dipping, maceration extract is impregnated on the carrier, flooded 5～20 hours down at 20～60 ℃; 60～180 ℃ of dryings 6～20 hours; Activation temperature is 450～900 ℃, total soak time 6～20 hours.
The soluble-salt of active component oxide can be the nitrate, acetate, sulfate, chloride of active component oxide etc., can use one or more preparation maceration extracts wherein, and maceration extract pH is 1.0～5.0; Adopt two steps or multistep dipping, add the surfactant of 0.01～0.1ml/l in the maceration extract, can be anionic, amphoteric or nonionic surface active agent, preferred sulfonic acid, sulphate esters class (as K12A, SCI65), polyoxyethylene-type (as 6501 classes, AEO-9).
Repeatedly dipping among the present invention refers to step impregnation behind the soluble-salt difference wiring solution-forming of various active component oxides to carrier; Also can take the soluble-salt of various active component oxide is made graded impregnation behind the mixed solution, repeatedly dipping adopts method in common, dipping, dry, activation dipping, drying, the such cyclic process of activation again, the maceration extract consumption preferably accounts for 20～70wt% of total maceration extract for the first time, generally all adopt the most frequently used dipping method in every respect, the present invention is not limited especially.
The interpolation surfactant can reduce the surface tension of maceration extract, improves wetability, impels active component to the diffusion of carrier inner duct, improves load factor, and makes active component be dispersed in the carrier surfaces externally and internally.
Activation (roasting) temperature is according to the decomposition temperature of active component salt, and the temperature of active component oxide and alumina support formation spinel structure is determined.
Adopt preparation method of the present invention, active component is dispersed in the surfaces externally and internally of catalyst granules, and catalyst granules center (sampled point radius 50～70 μ m) active component content is 50～70% of a particle surface content.
The present invention and existing similar catalyst relatively have following characteristics:
Preparation of Catalyst adopts multiple maceration, and to add low quantity of surfactant be auxiliary agent, adopts the catalyst of this method preparation, and active component is evenly distributed at the particle surfaces externally and internally.Electronic microscope photos shows, adopts the catalyst of single-steeping method preparation, and the content of particle center active component is less than 20% of surperficial content; Adopt preparation method of the present invention, the content of particle center active component can reach 50～70% of granule surface activity component.
Adopt the catalyst of the inventive method preparation, active component oxide and alumina catalyst support form stable spinel structure, and catalyst stability is good.XRD analysis shows, adopts the catalyst of single-steeping method preparation, and the active component oxide agglomerate is serious, is that the form with oxide adheres to catalyst surface substantially, has only a small amount of and carrier forms stable spinel structure; Adopt preparation method of the present invention, the active component oxide disperses evenly, and active component and carrier form stable spinel structure.Is example with zinc oxide as active component: adopt the catalyst of single-steeping method preparation, active component losss that come off easily, participate in primary first-order equation after, catalyst activity constituent content loss 70～80%; Adopt the catalyst performance stabilised of the present invention's preparation, use 300～500 hours repeatedly after, active component not have loss substantially.
Method for preparing catalyst involved in the present invention is simple, need not special installation and just can finish load, helps industrialization and amplifies.Catalyst is the solid-carrying type catalyst, has solved the problem that existing homogeneous catalyst reclaims difficulty, has improved catalyst stability.Adopt the catalyst of the inventive method preparation highly stable, the catalyst stable operation life-span can reach about 500 hours.Catalyst of the present invention has advantages of high catalytic activity to urea methanol solution phase reaction Synthesis of dimethyl carbonate, and dimethyl carbonate is stablized yield can reach 73.6%.
Description of drawings
Fig. 1 is the XRD spectra with the zinc nitrate solution single-steeping
Fig. 2 is the XRD spectra with twice dipping of zinc nitrate solution
The XRD determining condition:
The Germany Brooker D8ADVANCE X of company diffractometer
Tube voltage: 40kV electric current: 40mA
Scanning: 25 ℃ of 4 °～120 ° temperature of 0.02 ° of frequency 0.5s of step-length sweep limits
Cu K α 1 wavelength, abscissa is the angle of diffraction 2 θ among the figure, ordinate is a diffracted intensity
Symbol description among Fig. 1:
Symbol description among Fig. 2:
The condition of scanning, ■ gahnite-cubic-cell parameter-a8.08480-b8.08480-c8.08480-α 90.000-β 90.000-γ 90.000
As can be seen from the figure, make presoma with zinc nitrate, the catalyst activity component of single-steeping preparation exists with zinc oxide and two kinds of forms of gahnite, and active component comes off easily.And adopt preparation method of the present invention, the catalyst of twice dipping preparation, the complete and carrier formation gahnite structure of active component, catalyst performance stabilised.
The specific embodiment
The surfactant that is adopted in the catalyst preparation process is Beijingization friendly industry and trade Co., Ltd and Xingtai City auxiliary reagent factory product, and technical grade, other medicines are pure for analyzing without exception except that specified otherwise; Kinds of surfactants that embodiment adopts and number as shown in table 1ly, bearer number is as shown in table 2.
Table 1 uses surfactant types and numbering
| The surfactant title | Numbering | The surfactant title | Numbering |
| 6501(1∶2) | Surfactant 1 | SCI-65 | Surfactant 7 |
| AEO-9 | Surfactant 2 | K12A | Surfactant 8 |
| 6501(1∶1.5) | Surfactant 3 | MAP-K | Surfactant 9 |
| 6501(1∶1) | Surfactant 4 | APG-1200 | Surfactant 10 |
| APG-2000 | Surfactant 5 | AEO-9 | Surfactant 11 |
| CAB-35 | Surfactant 6 | AEO-7-9 | Surfactant 12 |
Table 2 bearer type and numbering
| Support shapes, kind | Bearer number | Al 2O 3Carrier character | ||||
| Size mm | Crystal formation | The aperture (
 |
Specific surface (m 2/g) | Specific pore volume (cm 3/L) | ||
| Microspheric form | 1 | φ3 | γ | 90～120 | 125.06 | 0.535 |
| Wafers | 2 | φ4×4 | γ | 70～125 | 98.75 | 0.637 |
| Trifolium-shaped | 3 | φ3 | γ | 65～113 | 136.45 | 1.325 |
Catalyst activity component of the present invention distributes and adopts electronic microscope photos, available instrument model philips XL-20 ESEM (SEM), at the catalyst granules center (sampled point radius 50 μ m), apart from center 1/3R place, respectively get 3 points apart from center 2/3R place, particle surface, detection of active component element percentage composition.
The said load factor of this patent all refers to the amount of active ingredients of unit mass carrier institute load, and active component content adopts atomic absorption method to measure.
The catalyst stable operation life-span is meant with a collection of catalyst, and the accumulation effective reaction time of catalytic reaction repeatedly in autoclave, each post catalyst reaction are used distilled water flushing half an hour.
Product adopts the gas-chromatography area to proofread and correct the normalization method analysis, and conversion rate of urea and dimethyl carbonate yield adopt following formula to calculate:
[Comparative Examples 1] Zinc oxide catalytic: adopt Zn (NO
3)
2.6H
2O made 800 ℃ of roastings in 3 hours.In the 500ml autoclave of being furnished with distillation column, add 300ml methyl alcohol and 11.7g urea, add catalyst 5.0g.Reaction pressure 1.5MPa, 180 ℃ of reaction temperatures were reacted 8 hours.The result is shown in table 19.
Pb (the NO of [Comparative Examples 2] preparation 20wt%
3)
2The aqueous solution, 10% ammoniacal liquor is made precipitating reagent, under the vigorous stirring two kinds of solution is slowly mixed, and leaves standstill aging filtration after 10 hours, and filter cake is dried to constant weight at 100 ℃, obtains the PbO catalyst in 5 hours in 700 ℃ of roastings in muffle furnace.Catalyst addition 5.0g and reacts in autoclave under last routine the same terms.The result is shown in table 19.
Zn (the NO of [Comparative Examples 3] preparation 60wt%
3)
2Solution 70ml regulates pH value 3.0, is impregnated under the room temperature on the 50g carrier 1, floods 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 3 hours from room temperature in 5 hours.Use the Zn (NO) of 50wt% through the catalyst of a step dipping
2Solution 50ml carries out double-steeping, drying and in 800 ℃ of constant temperature calcinings 3 hours.The gained catalyst consists of zinc oxide 33.6wt%, aluminium oxide 66.4wt%, and the catalyst activity constituent content distributes as shown in table 3.Catalyst addition 17.0g and reacts in autoclave under Comparative Examples 1 the same terms.The result is shown in table 19.
Table 3 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | K％ |
| The catalyst granules center | 84.52 | 13.58 | 1.91 |
| Apart from center 1/3R place | 84.67 | 12.98 | 2.35 |
| Apart from center 2/3R place | 84.05 | 14.05 | 1.89 |
| The catalyst granules surface | 5.01 | 94.77 | 0.23 |
Mg (the NO of [Comparative Examples 4] preparation 70wt%
3)
2Solution 50ml, the surfactant 1 of interpolation 0.03ml/l is regulated pH value 3.0, is impregnated under the room temperature on the 50g carrier 1, floods 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 3 hours from room temperature in 5 hours.The catalyst of the one step dipping Mg (NO of 40wt%
3)
2Solution (add surfactant 5) carries out double-steeping, drying and in 800 ℃ of constant temperature calcinings 3 hours.The gained catalyst consists of magnesia 29.8wt%, aluminium oxide 70.2wt%.Catalyst addition 17.2g and reacts in autoclave under Comparative Examples 1 the same terms.The result is shown in table 19.
Zn (the NO of [Comparative Examples 5] preparation 80wt%
3)
2Solution 65ml regulates pH value 2.0, the La (NO of preparation 30wt%
3)
3Solution 50ml regulates pH value 3.0.Under the room temperature at first with Zn (NO
3)
2Solution impregnation was flooded 2 hours in 60 ℃ of constant temperature to 50g carrier 2.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 3.5 hours from room temperature in 5 hours; Use identical method with La (NO then
3)
3Solution impregnation is on carrier, and dry, roasting obtains required catalyst.Catalyst consists of zinc oxide 31.7wt%, lanthana 12.6wt%, and aluminium oxide 55.7wt%, the catalyst activity constituent content distributes as shown in table 4.React in the autoclave, catalyst addition 16.4g and reacts in autoclave under Comparative Examples 1 the same terms.The result is shown in table 19.
Table 4 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | La％ | K％ |
| The catalyst granules center | 87.06 | 10.48 | 1.05 | 1.41 |
| Apart from center 1/3R place | 84.56 | 12.60 | 1.35 | 1.49 |
| Apart from center 2/3R place | 79.78 | 13.84 | 5.02 | 1.36 |
| The catalyst granules surface | 19.61 | 60.75 | 19.31 | 0.33 |
Zn (the NO of [Comparative Examples 6] preparation 80wt%
3)
2Solution 70ml, the surfactant 2 of interpolation 0.05ml/l is regulated pH value 3.0, is impregnated into 50g wafers θ-Al under the room temperature
2O
3On the carrier, carrier character is: aperture 50～86
, specific surface 106.25m
2/ g, specific pore volume 0.74cm
3/ L flooded 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 3 hours from room temperature in 5 hours.Use the Zn (NO of 50wt% through the catalyst of a step dipping
3)
2Solution 50ml carries out double-steeping, drying and in 800 ℃ of constant temperature calcinings 3 hours.The gained catalyst consists of zinc oxide 40.4wt%, aluminium oxide 59.6wt%.Catalyst addition 17.0g and reacts in autoclave under Comparative Examples 1 the same terms.The result is as shown in table 3.
[embodiment 1] prepares the Zn (NO of 85wt% respectively
3)
2Solution 70ml, the surfactant 1 of interpolation 0.05ml/l is regulated pH value 3.0.Zn (the NO of 50wt%
3)
2Solution 50ml, the surfactant 2 of interpolation 0.1ml/l is regulated pH value 3.0.Under the room temperature at first with the Zn (NO of 60wt%
3)
2Solution impregnation was flooded 2 hours in 60 ℃ to 50g carrier 1.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 3 hours from room temperature in 5 hours.The catalyst of the one step dipping Zn (NO) of 50wt%
2Solution carries out double-steeping, drying and in 800 ℃ of constant temperature calcinings 3 hours.The gained catalyst consists of zinc oxide 43.2wt%, aluminium oxide 56.8wt%, and the catalyst activity constituent content distributes as shown in table 5.
Table 5 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | K％ |
| The catalyst granules center | 40.61 | 58.96 | 0.43 |
| 1/3 place apart from the center | 35.83 | 63.66 | 0.51 |
| 2/3 place apart from the center | 20.37 | 79.60 | 0.04 |
| The catalyst granules surface | 6.77 | 92.92 | 0.31 |
In the 500ml autoclave of being furnished with distillation column, add 300ml methyl alcohol and 11.7g urea, add catalyst 14.5g.Reaction pressure 1.5MPa, 180 ℃ of reaction temperatures, 8 hours reaction time.The result is shown in table 19.
[embodiment 2] prepare the Pb (NO of 70wt% respectively
3)
2Solution 50ml, the surfactant 2 of interpolation 0.05ml/l, 40wt%Pb (NO
3)
2Solution 50ml adds 0.06ml/l surfactant 1, regulates pH value 3.0.Under the room temperature with the Pb (NO of 60wt%
3)
2Solution impregnation was flooded 2 hours in 60 ℃ of constant temperature to 50g carrier 2.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 5 hours from room temperature in 5 hours.The catalyst of the one step dipping Pb (NO of 40wt%
3)
2Solution carries out double-steeping, drying, and 800 ℃ of constant temperature calcinings 7 hours.The gained catalyst consists of lead oxide 31.2wt%, aluminium oxide 68.8wt%, and the catalyst activity constituent content distributes as shown in table 6.React in the autoclave, catalyst addition 16.8g, other conditions are with embodiment 1.The result is shown in table 19.
Table 6 catalyst activity constituent content distributes
| The position | Al％ | Pb％ | K％ |
| The catalyst granules center | 50.99 | 48.92 | 0.09 |
| 1/3 place apart from the center | 40.64 | 58.71 | 0.65 |
| 2/3 place apart from the center | 25.69 | 73.50 | 0.81 |
| The catalyst granules surface | 3.15 | 95.92 | 0.93 |
[embodiment 3] prepare the Ca (NO of 60wt% respectively
3)
2Solution 75ml, the surfactant 3 of interpolation 0.03ml/l, 40wt%Ca (NO
3)
2Solution 50ml adds 0.04ml/l surfactant 3, all regulates pH value 4.0.Under the room temperature with the Ca (NO of 60wt%
3)
2Solution impregnation was flooded 2 hours in 60 ℃ of constant temperature to 50g carrier 3.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 3.5 hours from room temperature in 5 hours.Catalyst 40wt%Ca (the NO of one step dipping
3)
2Solution carry out double-steeping, drying, and 800 ℃ of constant temperature calcinings 7 hours.Catalyst consists of calcium oxide 29.6wt%, aluminium oxide 70.4wt%, and the catalyst activity constituent content distributes as shown in table 7.React in the autoclave, catalyst addition 18.8g, other conditions are with embodiment 1.The result is shown in table 19.
Table 7 catalyst activity constituent content distributes
| The position | Al％ | Ca％ | K％ |
| The catalyst granules center | 49.11 | 50.86 | 0.03 |
| 1/3 place apart from the center | 35.90 | 63.69 | 0.41 |
| 2/3 place apart from the center | 25.37 | 74.19 | 0.44 |
| The catalyst granules surface | 7.89 | 91.30 | 0.81 |
Zn (the NO of [embodiment 4] preparation 80wt%
3)
2Solution 75ml, the surfactant 3 of interpolation 0.03ml/l is regulated pH value 3.0, the Pb (AC) of preparation 40wt%
2Solution 50ml, the surfactant 4 of interpolation 0.05ml/l is regulated pH value 4.0.Under the room temperature at first with Zn (NO
3)
2Be impregnated on the 50g carrier 1, flooded 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 3.5 hours from room temperature in 5 hours; The catalyst of one step dipping is with Pb (AC)
2Solution carries out double-steeping, drying, and obtains required catalyst in 5 hours with 800 ℃ of roastings.Catalyst consists of zinc oxide 29.6wt%, lead oxide 11.3wt%, and aluminium oxide 59.1wt%, the catalyst activity constituent content distributes as shown in table 8.React in the autoclave, catalyst addition 16.8g, other conditions are with embodiment 1.The result is shown in table 19.
Table 8 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | Pb％ | K％ |
| The catalyst granules center | 53.30 | 40.96 | 5.61 | 0.13 |
| 1/3 place apart from the center | 37.60 | 53.77 | 8.22 | 0.41 |
| 2/3 place apart from the center | 18.84 | 68.40 | 12.32 | 0.44 |
| The catalyst granules surface | 3.43 | 80.80 | 15.56 | 0.21 |
Zn (the NO of [embodiment 5] preparation 80wt%
3)
2Solution 80ml regulates pH value 2.0, adds the surfactant 5 of 0.03ml/l, the La (NO of preparation 30wt%
3)
3Solution 50ml, the surfactant 1 of interpolation 0.05ml/l is regulated pH value 3.0.Under the room temperature at first with Zn (NO
3)
2Be impregnated on the 50g carrier 2, flooded 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 3.5 hours from room temperature in 5 hours; Catalyst La (the NO of one step dipping
3)
3Solution floods, drying, and 850 ℃ of roastings obtained required catalyst in 8 hours.Catalyst consists of zinc oxide 30.7wt%, lanthana 10.6wt%, and aluminium oxide 58.7wt%, the catalyst activity constituent content distributes as shown in table 9.React in the autoclave, catalyst addition 15.4g, other conditions are with embodiment 1.The result is shown in table 19.
Table 9 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | La％ | K％ |
| The catalyst granules center | 41.60 | 48.96 | 9.42 | 0.02 |
| 1/3 place apart from the center | 32.83 | 53.66 | 13.08 | 0.43 |
| 2/3 place apart from the center | 20.47 | 69.60 | 9.80 | 0.13 |
| The catalyst granules surface | 8.77 | 82.92 | 16.67 | 0.10 |
Zn (the NO of [embodiment 6] preparation 80wt%
3)
2Solution 100ml regulates pH value 2.0, adds the surfactant 6 of 0.03ml/l, the Sn (NO of preparation 40wt%
3)
2Solution 60ml, the surfactant 8 of interpolation 0.05ml/l is regulated pH value 3.0.Under the room temperature at first with Zn (NO
3)
2Solution impregnation is to 50g carrier 2, and 60 ℃ of constant temperature flooded 2 hours.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 3.5 hours from room temperature in 5 hours; Catalyst Sn (the NO of one step dipping
3)
2Solution floods, drying, and 850 ℃ of roastings obtained required catalyst in 8 hours.Catalyst consists of zinc oxide 32.3wt%, tin oxide 11.6wt%, and aluminium oxide 56.1wt%, the catalyst activity constituent content distributes as shown in table 10.React in the autoclave, catalyst addition 16.2g, other conditions are with embodiment 1.The result is shown in table 19.
Table 10 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | Sn％ | K％ |
| The catalyst granules center | 45.30 | 39.86 | 14.81 | 0.03 |
| 1/3 place apart from the center | 32.76 | 54.86 | 11.87 | 0.51 |
| 2/3 place apart from the center | 19.30 | 66.30 | 13.96 | 0.44 |
| The catalyst granules surface | 8.60 | 78.41 | 12.68 | 0.31 |
Zn (the NO of [embodiment 7] preparation 80wt%
3)
2Solution 80ml, the surfactant 7 of interpolation 0.03ml/l is regulated pH value 2.0, the Mg (NO of preparation 40wt%
3)
2Solution 75ml, the surfactant 1 of interpolation 0.04ml/l is regulated pH value 3.0.Under the room temperature at first with Zn (NO
3)
2Be impregnated on the 50g carrier 2,60 ℃ of constant temperature flooded 2 hours.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 3.5 hours from room temperature in 5 hours; Catalyst Sn (the NO of one step dipping
3)
2Solution floods, drying, and 850 ℃ of roastings obtained required catalyst in 8 hours.Catalyst consists of zinc oxide 32.3wt%, tin oxide 11.6wt%, and aluminium oxide 56.1wt%, the catalyst activity constituent content distributes as shown in table 11.React in the autoclave, catalyst addition 16.2g, other conditions are with embodiment 1.The result is shown in table 19.
Table 11 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | Mg％ | K％ |
| The catalyst granules center | 41.86 | 49.86 | 7.72 | 0.56 |
| 1/3 place apart from the center | 32.67 | 56.54 | 10.31 | 0.48 |
| 2/3 place apart from the center | 19.88 | 69.41 | 10.37 | 0.34 |
| The catalyst granules surface | 6.67 | 80.82 | 12.30 | 0.21 |
Zn (the NO of [embodiment 8] preparation 80wt%
3)
2Solution 50ml regulates pH value 2.0, adds the surfactant 6 of 0.03ml/l; Cr (the NO of preparation 40wt%
3)
3Solution 60ml, the surfactant 1 of interpolation 0.05ml/l is regulated pH value 3.0.Under the room temperature at first with Zn (NO
3)
2Be impregnated on the 50g carrier 8, flooded 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 4 hours from room temperature in 5 hours; With identical method with Cr (NO
3)
3Solution impregnation is on carrier, and dry, roasting obtains required catalyst.Catalyst consists of zinc oxide 33.8wt%, chromium oxide 10.8wt%, and aluminium oxide 55.4wt%, the catalyst activity constituent content distributes as shown in table 12.React in the autoclave, catalyst addition 15.8g, other conditions are with embodiment 1.The result is shown in table 19.
Table 12 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | Cr％ | K％ |
| The catalyst granules center | 40.61 | 45.96 | 12.60 | 0.83 |
| 1/3 place apart from the center | 32.76 | 53.06 | 13.61 | 0.57 |
| 2/3 place apart from the center | 20.46 | 65.58 | 13.52 | 0.44 |
| The catalyst granules surface | 7.60 | 72.83 | 19.46 | 0.11 |
Zn (the NO of [embodiment 9] preparation 80wt%
3)
2Solution 85ml regulates pH value 2.0, adds the surfactant 3 of 0.03ml/l, the Zr (NO of preparation 30wt%
3)
2Solution 60ml, the surfactant 8 of interpolation 0.05ml/l is regulated pH value 3.0.Under the room temperature at first with Zn (NO
3)
2Be impregnated on the 50g carrier 9, flooded 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 4 hours from room temperature in 5 hours; With identical method with zr (NO
3)
2Solution impregnation is on carrier, and dry, roasting obtains required catalyst.Carrier adopts the microspheric form alumina support, and catalyst consists of zinc oxide 30.3wt%, zirconia 13.6wt%, and aluminium oxide 56.1wt%, the catalyst activity constituent content distributes as shown in table 13.React in the autoclave, catalyst addition 16.2g, other conditions are with embodiment 1.The result is shown in table 19.
Table 13 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | Zr％ | K％ |
| The catalyst granules center | 53.61 | 38.95 | 7.02 | 0.43 |
| 1/3 place apart from the center | 35.86 | 53.46 | 10.17 | 0.51 |
| 2/3 place apart from the center | 22.47 | 62.66 | 14.33 | 0.54 |
| The catalyst granules surface | 8.06 | 75.82 | 15.81 | 0.31 |
Zn (the NO of [embodiment 10] preparation 80wt%
3)
2Solution 75ml regulates pH value 2.0, adds the surfactant 4 of 0.03ml/l, the Mn (NO of preparation 40wt%
3)
2Solution 50ml, the surfactant 9 of interpolation 0.05ml/l is regulated pH value 3.0.Under the room temperature at first with Zn (NO
3)
2Be impregnated on the 50g carrier 10, flooded 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 4 hours from room temperature in 5 hours; With identical method with Mn (NO
3)
2Solution impregnation on carrier, drying, 800 ℃ of roastings obtain required catalyst.Catalyst consists of zinc oxide 34.6wt%, manganese oxide 12.3wt%, and aluminium oxide 53.1wt%, the catalyst activity constituent content distributes as shown in table 14.React in the autoclave, catalyst addition 16.2g, other conditions are with embodiment 1.The result is shown in table 19.
Table 14 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | Mn％ | K％ |
| The catalyst granules center | 39.61 | 49.43 | 10.43 | 0.53 |
| 1/3 place apart from the center | 30.03 | 55.05 | 14.51 | 0.41 |
| 2/3 place apart from the center | 20.07 | 65.45 | 14.04 | 0.44 |
| The catalyst granules surface | 6.82 | 76.56 | 16.31 | 0.31 |
Zn (the NO of [embodiment 11] preparation 80wt%
3)
2Solution 70ml regulates pH value 2.0, adds the surfactant 5 of 0.03ml/l; Cu (the NO of preparation 40wt%
3)
2Solution 50ml, the surfactant 9 of interpolation 0.05ml/l is regulated pH value 3.0.Under the room temperature at first with Zn (NO
3)
2Be impregnated on the 50g carrier 2, flooded 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 4 hours from room temperature in 5 hours; With identical method with Cu (NO
3)
2Solution impregnation on carrier, drying, 850 ℃ of roastings obtain required catalyst.Catalyst consists of zinc oxide 30.3wt%, cupric oxide 9.8wt%, and aluminium oxide 59.9wt%, the catalyst activity constituent content distributes as shown in Table 15.React in the autoclave, catalyst addition 16.2g, other conditions are with embodiment 1.The result is shown in table 19.
Table 15 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | Cu％ | K％ |
| The catalyst granules center | 40.65 | 53.06 | 5.86 | 0.43 |
| 1/3 place apart from the center | 30.65 | 60.86 | 7.98 | 0.51 |
| 2/3 place apart from the center | 20.41 | 69.23 | 10.32 | 0.04 |
| The catalyst granules surface | 6.58 | 82.30 | 10.31 | 0.31 |
Zn (the NO of [embodiment 12] preparation 80%
3)
2Solution 70ml regulates pH value 2.0, adds the surfactant 1 of 0.03ml/l; Pb (the NO of preparation 40wt%
3)
2Solution 50ml, the surfactant 4 of interpolation 0.05ml/l is regulated pH value 3.0; Sn (the NO of preparation 30wt%
3)
2Solution 50ml, the surfactant 6 of interpolation 0.05ml/l is regulated pH value 3.0.Under the room temperature at first with Zn (NO
3)
2Be impregnated on the 50g carrier 2, flooded 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 4 hours from room temperature in 5 hours; With identical method with Pb (NO
3)
2The solution solution impregnation adopts identical method drying on carrier, 500 ℃ of roastings 4 hours; Catalyst Sn (NO through twice dipping
3)
2Solution floods, and 800 ℃ of roastings obtained required catalyst in 4 hours, and catalyst consists of zinc oxide 30.3wt%, lead oxide 12.0%, and tin oxide 6.4wt%, aluminium oxide 51.3wt%, the catalyst activity constituent content distributes shown in table 16.React in the autoclave, catalyst addition 16.5g, other conditions are with embodiment 1.The result is shown in table 19.
Table 16 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | Pb％ | Sn％ | K％ |
| The catalyst granules center | 49.77 | 38.96 | 5.76 | 5.48 | 0.03 |
| 1/3 place apart from the center | 42.29 | 43.66 | 6.51 | 7.43 | 0.11 |
| 2/3 place apart from the center | 24.06 | 60.60 | 8.04 | 7.06 | 0.24 |
| The catalyst granules surface | 6.52 | 72.76 | 9.81 | 10.40 | 0.51 |
Zn (the NO of [embodiment 13] preparation 80wt%
3)
2Solution 70ml regulates pH value 2.0, adds the surfactant 11 of 0.03ml/l; Pb (the NO of preparation 40wt%
3)
2Solution 60ml, the surfactant 1 of interpolation 0.05ml/l is regulated pH value 3.0; La (the NO of preparation 30wt%
3)
3Solution 50ml, the surfactant 8 of interpolation 0.05ml/l is regulated pH value 3.0.Under the room temperature at first with Zn (NO
3)
2Be impregnated on the 50g carrier 3, flooded 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 550 ℃, constant temperature calcining 4 hours from room temperature in 5 hours; The catalyst of single-steeping Pb (NO
3)
2Solution floods, and adopts identical method to carry out drying, and La (NO is used in 500 ℃ of roastings after 4 hours
3)
3Solution floods, and 800 ℃ of roastings 6 hours obtain required catalyst.Catalyst consists of zinc oxide 30.3wt%, lead oxide 12.0wt%, and lanthana 6.4wt%, aluminium oxide 51.3wt%, the catalyst activity constituent content distributes shown in table 17.React in the autoclave, catalyst addition 16.8g, other conditions are with embodiment 1.The result is shown in table 19.
Table 17 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | Pb％ | La％ | K％ |
| The catalyst granules center | 46.33 | 42.20 | 6.44 | 4.83 | 0.20 |
| 1/3 place apart from the center | 37.68 | 48.72 | 7.56 | 5.61 | 0.43 |
| 2/3 place apart from the center | 22.69 | 62.40 | 8.46 | 5.84 | 0.61 |
| The catalyst granules surface | 5.69 | 76.03 | 8.78 | 8.76 | 0.74 |
Zn (the NO of [embodiment 14] preparation 80wt%
3)
2Solution 50ml regulates; Pb (the NO of 40wt%
3)
2Solution 50ml; La (the NO of preparation 40wt%
3)
3Solution 50ml.Three kinds of solution are mixed the back fully regulate pH value 3.0, add the surfactant 12 of 0.03ml/l.The mixed solution of at first getting 60ml is impregnated on the 50g carrier 3, floods 2 hours in 60 ℃ of constant temperature.At the uniform velocity be warming up to 150 ℃ of dryings 10 hours from 80 ℃.Rose to 500 ℃, constant temperature calcining 4 hours from room temperature in 5 hours; The catalyst of single-steeping floods with the mixed solution of 90ml, adopts identical method to carry out drying, and 900 ℃ of roastings 6 hours obtain required catalyst.Catalyst consists of zinc oxide 36.3wt%, lead oxide 11.5wt%, and lanthana 4.5wt%, aluminium oxide 47.4wt%, the catalyst activity constituent content distributes shown in table 18.React in the autoclave, catalyst addition 16.8g, other conditions are with embodiment 1.The result is shown in table 19.
Table 18 catalyst activity constituent content distributes
| The position | Al％ | Zn％ | Pb％ | La％ | K％ |
| The catalyst granules center | 42.02 | 47.34 | 5.76 | 4.68 | 0.20 |
| 1/3 place apart from the center | 36.79 | 50.36 | 7.06 | 5.56 | 0.23 |
| 2/3 place apart from the center | 20.36 | 63.74 | 8.58 | 7.08 | 0.24 |
| The catalyst granules surface | 5.61 | 76.61 | 9.82 | 7.76 | 0.20 |
Table 19 implementation evaluation result
| Project | Conversion rate of urea (%) | DMC yield (%) | Life-span (h) |
| Comparative Examples 1 | 100 | ?21.3 | Fine catalyst can't reclaim |
| Comparative Examples 2 | 100 | ?19.2 | Fine catalyst can't reclaim |
| Comparative Examples 3 | 100 | ?15.6 | 8 |
| Comparative Examples 4 | 100 | ?10.3 | 8 |
| Comparative Examples 5 | 100 | ?48.3 | 8 |
| Comparative Examples 6 | 100 | ?40.2 | 8 (loss of active component) |
| Embodiment 1 | 100 | ?46.3 | 500 |
| Embodiment 2 | 100 | ?45.8 | 400 |
| Embodiment 3 | 100 | ?51.6 | 300 |
| Embodiment 4 | 100 | ?59.8 | 400 |
| Embodiment 5 | 100 | ?55.4 | 400 |
| Embodiment 6 | 100 | ?51.3 | 260 |
| Embodiment 7 | 100 | ?48.3 | 400 |
| Embodiment 8 | 100 | ?47.6 | 300 |
| Embodiment 9 | 100 | ?48.8 | 500 |
| |
100 | ?40.9 | 500 |
| Embodiment 11 | 100 | ?51.2 | 500 |
| |
100 | ?62.5 | 450 |
| Embodiment 13 | 100 | ?73.6 | 450 |
| Embodiment 14 | 100 | ?65.6 | 500 |
Claims (9)
1. catalyst for preparing dimethyl carbonate by using urea alcoholysis, it is characterized in that: carrier is γ-Al
2O
3, accounting for 50～80wt% of whole catalyst, all the other are active component; Main active component is at least a among ZnO, CaO, the PbO, accounts for 80～100wt% of gross activity component; The specific area of catalyst is 150～350m
2/ g, specific pore volume are 0.5～2.0cm
3/ L, pore-size distribution are 50～150
The catalyst activity constituent content distributes and adopts electronic microscope photos, the sampled point radius is 50～70 μ m, catalyst granules accounts for 65～80% of surface active composition content apart from center 1/3R place active component content, account for 80～90% of surface active composition content apart from center 2/3R place active component content, R is the distance of catalyst granules center to catalyst surface.
2. catalyst according to claim 1 is characterized in that: main active component is that ZnO is or/and PbO.
3. catalyst according to claim 1 is characterized in that: also contain in the catalyst activity component content account for the gross activity component 0～20wt% help component, be selected from La
2O
3, MgO, Cr
2O
3, ZrO, MnO
2, SnO
2, among the CuO one or more.
4. catalyst according to claim 3 is characterized in that: helping component in the active component is La
2O
3Or/and SnO
2
5. catalyst according to claim 1 is characterized in that: main active component and γ-Al
2O
3Form spinel structure.
6. catalyst according to claim 1 is characterized in that: catalyst granules center active component content accounts for 50～65% of surface active composition content.
7. described Preparation of catalysts method of claim 1 is characterized in that getting the soluble-salt preparation maceration extract of active component oxide, and regulating pH is 1.0～5.0; Add anion, nonionic or the amphoteric surfactant of 0.01～0.1ml/l in the maceration extract, and mix; Employing multistep dipping is impregnated into maceration extract on the carrier, descends total dip times 5～20 hours at 20～60 ℃; 60～180 ℃ of dryings 6～20 hours; Activation temperature is 450～900 ℃, total soak time 6～20 hours.
8. according to the described Preparation of catalysts method of claim 7, it is characterized in that: the soluble-salt of active component oxide is nitrate, acetate, sulfate or the chloride of active component oxide.
9. according to the described Preparation of catalysts method of claim 7, it is characterized in that: the surfactant that adds in the maceration extract is the ester class or the polyoxyethylene-type surfactant of sulfonic acid, sulfate.
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| CN102553598A (en) * | 2010-12-23 | 2012-07-11 | 中国科学院兰州化学物理研究所 | Catalyst for synthetizing benzyl carbamate, preparation method and application |
| CN103288645B (en) * | 2012-02-23 | 2016-03-16 | 亚申科技研发中心（上海）有限公司 | Separation of dimethyl ether in the technique of alcoholysis of urea co-producing dimethyl carbonate and dme also reclaims the method for ammonia |
| CN103623802A (en) * | 2012-08-27 | 2014-03-12 | 亚申科技研发中心（上海）有限公司 | Method for simultaneously producing dimethyl carbonate and dimethyl ether through urea alcoholysis process, catalyst used thereby, and preparation method of catalyst |
| CN103012210B (en) * | 2012-12-13 | 2014-09-17 | 黄河三角洲京博化工研究院有限公司 | Preparation method of isophorone diamidoformate |
| CN108586243B (en) * | 2018-03-30 | 2021-07-16 | 昆明理工大学 | A kind of method for indirect synthesis of organic carbonate with carbon dioxide and organic amine |
| CN111318278A (en) * | 2018-12-13 | 2020-06-23 | 中国石油化工股份有限公司 | Preparation method of catalyst for preparing cyclohexane-1, 2-dioctyl phthalate |
| CN110479236A (en) * | 2019-09-06 | 2019-11-22 | 山东科技大学 | A kind of carbon dioxide and methanol-fueled CLC dimethyl carbonate catalyst and preparation method |
| CN114917891A (en) * | 2022-05-26 | 2022-08-19 | 山东海科新源材料科技股份有限公司 | Synthetic method and application of non-noble metal supported catalyst |
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|---|---|---|---|---|
| US4128503A (en) * | 1976-03-31 | 1978-12-05 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Catalyst for purifying exhaust and waste gases and method for preparation thereof |
| CN1597096A (en) * | 2004-08-27 | 2005-03-23 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing dimethyl carbonate from ured and methanol and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4128503A (en) * | 1976-03-31 | 1978-12-05 | Nippon Shokubai Kagaku Kogyo Co. Ltd. | Catalyst for purifying exhaust and waste gases and method for preparation thereof |
| CN1597096A (en) * | 2004-08-27 | 2005-03-23 | 中国科学院山西煤炭化学研究所 | Catalyst used for synthesizing dimethyl carbonate from ured and methanol and its preparation method and application |
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