CN111153768A - Synthetic method of isohexide - Google Patents
Synthetic method of isohexide Download PDFInfo
- Publication number
- CN111153768A CN111153768A CN202010072809.0A CN202010072809A CN111153768A CN 111153768 A CN111153768 A CN 111153768A CN 202010072809 A CN202010072809 A CN 202010072809A CN 111153768 A CN111153768 A CN 111153768A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- diacetone alcohol
- temperature
- isohexide
- hours
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000010189 synthetic method Methods 0.000 title description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims abstract description 160
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 42
- 239000001257 hydrogen Substances 0.000 claims abstract description 42
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 17
- 239000006229 carbon black Substances 0.000 claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052737 gold Inorganic materials 0.000 claims abstract description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 4
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 4
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 49
- 239000012265 solid product Substances 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 31
- 238000001994 activation Methods 0.000 claims description 22
- 230000004913 activation Effects 0.000 claims description 21
- 230000009467 reduction Effects 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 238000001914 filtration Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 15
- 150000002431 hydrogen Chemical class 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 12
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003223 protective agent Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 20
- 229910052681 coesite Inorganic materials 0.000 description 13
- 229910052906 cristobalite Inorganic materials 0.000 description 13
- 239000000377 silicon dioxide Substances 0.000 description 13
- 229910052682 stishovite Inorganic materials 0.000 description 13
- 229910052905 tridymite Inorganic materials 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 238000004817 gas chromatography Methods 0.000 description 12
- 238000011065 in-situ storage Methods 0.000 description 12
- 238000005086 pumping Methods 0.000 description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910003286 Ni-Mn Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910017709 Ni Co Inorganic materials 0.000 description 6
- 229910003267 Ni-Co Inorganic materials 0.000 description 6
- 229910003262 Ni‐Co Inorganic materials 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002645 Ni-Rh Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZRPORXYFFFAMLA-UHFFFAOYSA-N 2,4,4,6-tetramethyl-1,3-dioxane Chemical compound CC1CC(C)(C)OC(C)O1 ZRPORXYFFFAMLA-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 229910017566 Cu-Mn Inorganic materials 0.000 description 1
- 229910017871 Cu—Mn Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010364 biochemical engineering Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/892—Nickel and noble metals
-
- B01J35/394—
-
- 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
Abstract
The invention discloses a method for synthesizing isohexane glycol, which takes diacetone alcohol and hydrogen as raw materials to carry out hydrogenation reaction in the presence of a catalyst to prepare the isohexane glycol, wherein the catalyst is a supported double-component heterogeneous catalyst consisting of an active component and a carrier, the first active component of the catalyst is Ni or Cu, the second active component of the catalyst is one of Rh, Au, Re, La, Co, Mn or Ag, and the carrier is one or more than two of active carbon, white carbon black and gas phase alumina. The special catalyst is used in the reaction for preparing the isohexide by catalyzing the hydrogenation of the diacetone alcohol, the catalyst has extremely high stability and catalytic activity, the yield of the isohexide is high, the utilization rate of active components is high, the 100 percent conversion rate and 99.9 percent selectivity can be achieved under mild reaction conditions without adding a protective agent, and the catalyst is continuously stable for 500 hours and is not obviously deactivated.
Description
Technical Field
The invention relates to the technical field of compound synthesis, in particular to a method for synthesizing isohexide.
Background
Isohexylene glycol (MPD for short), chinese name: 2-methyl-2, 4-pentanediol, a colorless, transparent, slightly viscous liquid, with a slightly fresh, sweet and fragrant smell. As a fine chemical product with wide application, the isohexide is widely applied in the fields of building materials, cosmetics, textiles, pesticides, coatings, biochemical engineering, organic synthesis and the like, and is mainly used as a solvent, a coupling agent, an emulsifier, a penetrating agent, a stabilizer and the like. According to different routes of raw materials, the existing synthesis processes of isohexide are divided into two types:
(1) the acetone condensate diacetone alcohol is used as a raw material and is synthesized by a catalytic hydrogenation method;
(2) the compound is prepared by taking 2,4,4, 6-tetramethyl-1, 3-dioxacyclohexane as a raw material and decomposing methanol.
Compared with the two methods, the first method has wide sources of raw materials, low price and easy realization, thereby gaining wide attention. However, in the process of synthesizing isohexide by hydrogenation reduction using diacetone alcohol as raw material, the preparation of high performance hydrogenation catalyst is a key link for realizing the final industrial application of the reaction.
Patent CN1066608A reports a catalyst for hydrogenation of diacetone alcohol, in which highly dispersed nickel (Ni) metal supported catalyst (Ni/SiO) is prepared by metal vapor method2) The catalyst has the conversion rate of diacetone alcohol of 95 percent in a high-pressure reaction kettle, and the selectivity of the target product, namely, the isohexide, is only 50 percent. This method has not received much attention at the beginning of the report because the selectivity was too low.
Patents CN1228354A and CN1565730A have prepared highly dispersed heterogeneous nickel-based heterogeneous catalysts using nickel-aluminum alloy, which have a target product yield of 85% in the course of diacetone alcohol hydrogenation reaction. However, the preparation process of the series of catalysts is complex, a large amount of NaOH strong base solution is needed, the environmental pollution is serious, and the series of catalysts are not suitable for pilot scale production and industrial production.
Patents CN102329193B and CN107235825A respectively use raney nickel and hydroxyapatite as carrier to catalyze the hydrogenation reaction of diacetone alcohol to obtain excellent reaction results. The report in patent CN102329193B shows that a large amount of alkaline auxiliary agent needs to be added during the reaction process to obtain satisfactory catalytic reaction results, which will greatly increase the cost of subsequent separation and environmental management. Both the two reaction processes adopt an intermittent reaction kettle process, and stability data of the catalyst is not given, so that the scale-up production is not facilitated in the industrial application process, and the inactivation of the catalyst can greatly increase the production cost. Based on the previous report, the patent CN104549425B developed a molecular sieve-supported nickel-based heterogeneous catalyst which can stably run for 500 hours on a fixed bed reaction bed and still has excellent catalytic performance. However, the catalytic performance of the catalyst is reduced compared with the previous reports, which is probably because the side reaction in the reaction process is enhanced due to the fact that the pH value of the molecular sieve carrier is not easy to control.
In view of various problems in the reported patents, the excellent catalytic performance and the catalyst stability cannot be effectively unified, so that the catalyst which has the excellent catalytic performance and can operate for a long period with high stability is developed and combined with a continuous reaction process, the isohexide is prepared by hydrogenating diacetone alcohol, the industrial application requirement can be better met, and the short plate in the isohexide production in China at present can be timely solved.
Disclosure of Invention
The invention aims to provide a method for synthesizing isohexide, which aims to solve the defects of the prior art.
The invention adopts the following technical scheme:
a process for synthesizing isohexide includes such steps as hydrogenating diacetone alcohol and hydrogen in the presence of catalyst to obtain isohexide,
the catalyst is a supported double-component heterogeneous catalyst consisting of active components and a carrier, wherein the first active component of the catalyst is Ni or Cu, the second active component of the catalyst is one of Rh, Au, Re, La, Co, Mn or Ag, and the carrier is one or more than two of active carbon, white carbon black and fumed alumina; the content of the first active component is 0.1-30% of the mass of the catalyst, the content of the second active component is 0.01-10% of the mass of the catalyst, and the balance is a carrier; the supported bi-component heterogeneous catalyst is prepared by the following steps:
(1) mixing the soluble salt of the first main active component and the soluble salt of the second active component with the formula amount, deionized water and the carrier with the formula amount to prepare a mixed solution;
(2) dropwise adding a certain amount of strong ammonia water into the mixed solution prepared in the step (1) until the pH value is 8.5-13.5;
(3) stirring the mixed solution obtained in the step (2) at room temperature for 1-24 hours;
(4) stirring the mixed solution obtained in the step (3) at the temperature of 60-100 ℃ for 2-24 hours;
(5) filtering the mixed solution obtained in the step (4) to obtain a solid product, washing the obtained solid product with deionized water, and then drying the solid product at the temperature of 100 ℃ and 150 ℃ for 2 to 24 hours; then roasting at 200-800 ℃ for 2-24 hours to obtain the supported bi-component heterogeneous catalyst.
Further, the content of the first active component is 5-25% of the mass of the catalyst, and the content of the second active component is 0.1-5% of the mass of the catalyst.
Further, the supported bi-component heterogeneous catalyst needs to be subjected to reduction activation treatment before use, and the reduction activation treatment conditions are as follows: the temperature is 120-450 ℃, the pressure is 0.1-2.0 MPa, and the volume space velocity of hydrogen is 500-3000 h-1The treatment time is 1-120 h.
Further, the method for preparing the isohexide by taking diacetone alcohol and hydrogen as raw materials and carrying out hydrogenation reaction in the presence of a catalyst comprises the following steps: adding diacetone alcohol raw material into a mixer to mix with hydrogen, and then reacting in a reactor with certain temperature, pressure and catalyst to obtain a product, wherein the reaction conditions are as follows:
the reaction pressure is 0.5-10.0 MPa, the reaction temperature is 30-230 ℃, the molar ratio of hydrogen to diacetone alcohol is 1: 1-150: 1, and the liquid volume of diacetone alcohol is emptyThe speed is 0.1-6.0 h-1。
Further, the reaction pressure is 1.5-6.0 MPa, the reaction temperature is 60-120 ℃, the molar ratio of hydrogen to diacetone alcohol is 2: 1-10: 1, and the liquid volume space velocity of diacetone alcohol is 0.1-2.0 h-1。
Further, the reactor is a fixed bed reactor or a slurry bed reactor.
Further, the reactor is a fixed bed reactor.
The invention has the beneficial effects that:
1. the special catalyst is used in the reaction for preparing the isohexide by catalyzing the hydrogenation of diacetone alcohol, the catalyst is simple in preparation method, green and pollution-free, good in preparation repeatability, extremely high in stability and catalytic activity, high in yield of the isohexide, high in active component utilization rate, capable of achieving 100% conversion rate and 99.9% selectivity under mild reaction conditions without adding a protective agent, and continuous and stable for 500 hours, and does not obviously inactivate the catalyst. The invention has simple separation of reaction products and catalysts, simple reaction flow, reduces one-time investment and production cost of production and subsequent separation devices, and is easy to realize large-scale continuous industrial application.
2. The supported double-component heterogeneous catalyst prepared by the invention has the advantages that the double-active components are uniformly dispersed on the surface of the carrier, the dispersibility is high, and the double-active components are cooperatively catalyzed, so that diacetone alcohol and hydrogen molecules can be closely and fully contacted with double-active sites, and the catalytic hydrogenation efficiency is improved; in the preparation process of the catalyst, ammonia water uniformly acts with the carrier and the active component for a long time, so that the acting force between the active component and the carrier is enhanced, the agglomeration and sintering of the active component in the reaction process can be inhibited, and the stability of the catalyst is improved; in addition, the double components are used for concerted catalysis, the reaction condition is mild, and the selectivity of a target product is improved; the design of the high-performance catalytic reaction system avoids the addition of a large amount of protective agents in the reaction process, and the cost of later separation and purification is reduced by combining the use of a continuous fixed bed reaction process.
3. According to the invention, ammonia water is added into a precursor solution in advance during the preparation of the catalyst, and then ammonia is uniformly volatilized from a mixed system by a stirring and heating method, so that the ammonia in the whole catalyst preparation system is uniformly distributed, the active components are uniformly distributed on a carrier in the catalyst preparation process, and in addition, strong interaction can be generated between the active metal component salt and the nano-grade carrier in the precipitation process, so that the effect of highly dispersing the metal active components is achieved. A closely contacted interface is formed between the second active group and the first active component Ni or Cu in the catalyst preparation process, and the electron transfer between different components on the interface provides convenience for improving the electron transfer in the hydrogenation reaction process and accelerates the reaction process.
4. The activation method of the supported double-component heterogeneous catalyst is continuous activation, can take away a large amount of water generated in the activation process in time, and improves the mechanical strength of the catalyst.
5. The reactor is a continuous reactor, and is relative to a batch reactor, so that continuous production can be realized, the production safety is ensured, and the reactor is a proposal vigorously advocated by the state at present; secondly, a large amount of labor force can be liberated, and the production efficiency is improved.
Detailed Description
The present invention will be further explained with reference to examples. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
A method for synthesizing isohexane glycol, which takes diacetone alcohol and hydrogen as raw materials to prepare the isohexane glycol by hydrogenation reaction in the presence of a catalyst, comprises the following steps: adding diacetone alcohol raw material into a mixer to mix with hydrogen, and then reacting in a reactor with certain temperature, pressure and catalyst to obtain a product, wherein the reaction conditions are as follows:
the reaction pressure is 0.5-10.0 MPa, preferably 1.5-6.0 MPa, the reaction temperature is 30-230 ℃, preferably 60-120 ℃, the molar ratio of hydrogen to diacetone alcohol is 1: 1-150: 1, preferably 2: 1-10: 1, and the liquid volume space velocity of diacetone alcohol is 0.1-6.0 h-1Preferably 0.1 to 2.0 hours-1(ii) a The reactor is a fixed bed reactor or a slurry bed reactor, preferably a fixed bed reactor.
The catalyst is a supported double-component heterogeneous catalyst consisting of active components and a carrier, wherein the first active component of the catalyst is Ni or Cu, the second active component of the catalyst is one of Rh, Au, Re, La, Co, Mn or Ag, and the carrier is one or more than two of active carbon, white carbon black and fumed alumina; the content of the first active component is 0.1-30% of the mass of the catalyst, preferably 5-25%, the content of the second active component is 0.01-10% of the mass of the catalyst, preferably 0.1-5%, and the balance is a carrier; the supported bi-component heterogeneous catalyst is prepared by the following steps:
(1) mixing the soluble salt of the first main active component and the soluble salt of the second active component with the formula amount, deionized water and the carrier with the formula amount to prepare a mixed solution;
(2) dropwise adding a certain amount of strong ammonia water into the mixed solution prepared in the step (1) until the pH value is 8.5-13.5;
(3) stirring the mixed solution obtained in the step (2) at room temperature for 1-24 hours;
(4) stirring the mixed solution obtained in the step (3) at the temperature of 60-100 ℃ for 2-24 hours;
(5) filtering the mixed solution obtained in the step (4) to obtain a solid product, washing the obtained solid product with deionized water, and then drying the solid product at the temperature of 100 ℃ and 150 ℃ for 2 to 24 hours; then roasting at 200-800 ℃ for 2-24 hours to obtain the supported bi-component heterogeneous catalyst.
The supported bi-component heterogeneous catalyst needs to be subjected to reduction activation treatment before use, and the reduction activation treatment conditions are as follows: the temperature is 120-450 ℃, the pressure is 0.1-2.0 MPa, and the volume space velocity of hydrogen is 500-3000 h-1The treatment time is 1-120 h.
The activated carbon, the white carbon black (coconut shell) and the fumed alumina related to the following examples are all purchased from Shandong Li Hua New Material Co., Ltd and are all in nano-scale.
Example 1
Mixing 10.0g of nickel nitrate and 1.0g of cobalt nitrate with 150ml of deionized water and 10.0g of white carbon black to prepare a mixed solution; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solution until the pH value is 12.0; stirring at room temperatureMixing the mixed solution for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then transferring the mixture into a muffle furnace to roast the mixture for 8 hours at the temperature of 600 ℃ to obtain the catalyst Ni-Co/SiO2。
Taking the above Ni-Co/SiO2Catalyst 1.0g (ca. 2ml) was charged to a fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump to be fully mixed with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.g.h of the catalyst, and adjusting the H in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 99.8 percent, and the selectivity of the isohexide is 98.8 percent.
Example 2
Mixing 10.0g of nickel nitrate and 1.0g of silver nitrate with 150ml of deionized water and 10.0g of white carbon black to prepare a mixed solution; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solution until the pH value is 12.0; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then transferring the mixture into a muffle furnace to be roasted for 8 hours at the temperature of 600 ℃ to obtain the catalyst of Ni-Ag/SiO2。
Taking the above Ni-Ag/SiO2Catalyst 1.0g (ca. 2ml) was charged to a fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump, fully mixing the diacetone alcohol with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.h of the catalyst,h in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 90.8 percent, and the selectivity of the isohexide is 98.8 percent.
Example 3
Mixing 10.0g of nickel nitrate and 1.0g of lanthanum nitrate with 150ml of deionized water and 10.0g of white carbon black to prepare a mixed solution; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solution until the pH value is 12.0; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then transferring the mixture into a muffle furnace to be roasted for 8 hours at the temperature of 600 ℃ to obtain the catalyst Ni-La/SiO2。
Taking the Ni-La/SiO2Catalyst 1.0g (ca. 2ml) was charged to a fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump to be fully mixed with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.g.h of the catalyst, and adjusting the H in the reaction system2The reaction was carried out while controlling the flow rate at 50mL/min (example H)2And diacetone alcohol in a molar ratio of 10.0:1), the reaction time was 60 hours, and samples were taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 92.5 percent, and the selectivity of the isohexide is 98.9 percent.
Example 4
Mixing 10.0g of nickel nitrate and 0.5g of rhodium trichloride with 150ml of deionized water and 10.0g of white carbon black to prepare a mixed solution; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixture liquid until the pH value is 12.0; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; transferring to a muffle furnace to roast at 600 DEG CThe catalyst is Ni-Rh/SiO after 8 hours2。
Taking the Ni-Rh/SiO2Catalyst 1.0g (ca. 2ml) was charged to a fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump to be fully mixed with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.g.h of the catalyst, and adjusting the H in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 100 percent, and the selectivity of the isohexide is 99.9 percent.
Example 5
Mixing 10.0g of nickel nitrate and 0.3g of ammonium perrhenate with 150ml of deionized water and 10.0g of white carbon black to prepare a mixed solution; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solution until the pH value is 12.0; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then transferring the mixture into a muffle furnace to roast the mixture for 8 hours at the temperature of 600 ℃ to obtain the catalyst Ni-Re/SiO2。
Taking the above Ni-Re/SiO2Catalyst 1.0g (ca. 2ml) was charged to a fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump to be fully mixed with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.g.h of the catalyst, and adjusting the H in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. Diacetone alcohol hydrogenation reaction, diacetone alcohol conversion rate 99.9%, isohexaneThe diol selectivity was 99.8%.
Example 6
Mixing 10.0g of nickel nitrate and 0.8g of manganese nitrate with 150ml of deionized water and 10.0g of white carbon black to prepare a mixed solution; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solution until the pH value is 12.3; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then transferring the mixture into a muffle furnace to roast the mixture for 8 hours at the temperature of 600 ℃ to obtain the catalyst Ni-Mn/SiO2。
Taking the Ni-Mn/SiO2Catalyst 1.0g (ca. 2ml) was charged to a fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump to be fully mixed with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.g.h of the catalyst, and adjusting the H in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 100.0 percent, and the selectivity of the isohexide is 99.8 percent.
Example 7
Mixing 10.0g of nickel nitrate and 1.0g of cobalt nitrate with 150ml of deionized water and 10.0g of vapor phase aluminum oxide to prepare a mixed solution; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solution until the pH value is 13.0; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then transferring the mixture into a muffle furnace to roast the mixture for 8 hours at the temperature of 600 ℃ to obtain the catalyst Ni-Co/Al2O3。
Taking the above Ni-Co/Al2O3Catalyst 1.0g (ca. 2ml) was charged to a fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment, and the conditions of the reduction activation treatment areThe temperature is 450 ℃, the pressure is 0.3MPa, and the volume space velocity of hydrogen is 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump to be fully mixed with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.g.h of the catalyst, and adjusting the H in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 99.7 percent, and the selectivity of the isohexide is 99.2 percent.
Example 8
Mixing 10.0g of nickel nitrate and 1.0g of cobalt nitrate with 150ml of deionized water and 10.0g of active carbon AC to prepare a mixed solution; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solution until the pH value is 12.0; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then the mixture is transferred to a muffle furnace to be roasted for 8 hours at the temperature of 600 ℃ to obtain the catalyst Ni-Co/AC.
1.0g (about 2ml) of the above Ni-Co/AC catalyst was charged into a fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump to be fully mixed with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.g.h of the catalyst, and adjusting the H in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 100.0 percent, and the selectivity of the isohexide is 99.6 percent.
Example 9
Mixing 10.0g of nickel nitrate and 1.2g of chloroauric acid with 150ml of deionized water and 10.0g of white carbon black to prepare a mixed solution; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solution untilThe pH was 12.0; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then transferring the mixture into a muffle furnace to roast the mixture for 8 hours at the temperature of 600 ℃ to obtain the catalyst Ni-Au/SiO2。
Taking the Ni-Au/SiO2Catalyst 1.0g (ca. 2ml) was charged to a fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump to be fully mixed with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.g.h of the catalyst, and adjusting the H in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 93.8 percent, and the selectivity of the isohexide is 99.3 percent.
Example 10
Preparing a mixed solution by taking 10.0g of nickel nitrate, 0.8g of manganese nitrate, 150ml of deionized water, 10.0g of white carbon black and 5g of gas-phase alumina; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solution until the pH value is 12.3; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then transferring the mixture into a muffle furnace to roast the mixture for 8 hours at the temperature of 600 ℃ to obtain the catalyst Ni-Mn/SiO2-Al2O3。
Taking the Ni-Mn/SiO2-Al2O3Catalyst 1.0g (ca. 2ml) was charged to a fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol with high pressure pumpMixing with hydrogen in a mixer, regulating the liquid volume space velocity of diacetone alcohol to 0.5 g/g.h, and reacting in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 100.0 percent, and the selectivity of the isohexide is 95.8 percent.
Example 11
Preparing a mixed solution by taking 10.0g of nickel nitrate, 0.8g of manganese nitrate, 150ml of deionized water, 10.0g of white carbon black, 3g of gas-phase aluminum oxide and 4g of activated carbon; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solution until the pH value is 12.3; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then transferring the mixture into a muffle furnace to roast the mixture for 8 hours at the temperature of 600 ℃ to obtain the catalyst Ni-Mn/SiO2-Al2O3-AC。
Taking the Ni-Mn/SiO2-Al2O31.0g (ca. 2ml) of AC catalyst was charged in the fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump to be fully mixed with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.g.h of the catalyst, and adjusting the H in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 100.0 percent, and the selectivity of the isohexide is 96.8 percent.
Example 12
Preparing a mixed solution by taking 7.4g of copper nitrate, 0.8g of manganese nitrate, 150ml of deionized water, 10.0g of white carbon black, 3g of gas-phase aluminum oxide and 4g of activated carbon; a certain amount of strong ammonia water is taken at room temperature and is dripped into the mixed solutionTo a pH of 12.3; stirring the mixed solution at room temperature for 10 hours; then raising the temperature to 100 ℃ at the speed of 1 ℃/min, and stirring for 2 hours; filtering and washing the obtained solid product, and then drying the solid product for 24 hours at the temperature of 100 ℃; then transferring the mixture into a muffle furnace to roast the mixture for 8 hours at the temperature of 600 ℃ to obtain the catalyst Ni-Mn/SiO2-Al2O3-AC。
Taking the above Cu-Mn/SiO2-Al2O31.0g (ca. 2ml) of AC catalyst was charged in the fixed bed reactor. Before use, the raw materials are subjected to in-situ reduction activation treatment under the conditions of temperature of 450 ℃, pressure of 0.3MPa and hydrogen volume space velocity of 1000h-1And the treatment time is 12 h. And when the temperature in the reactor is naturally reduced to 120 ℃, increasing the pressure to 2.0MPa, and waiting for the system to be stable. Pumping diacetone alcohol into a mixer through a high-pressure pump to be fully mixed with hydrogen, adjusting the liquid volume space velocity of the diacetone alcohol to be 0.5 g/g.g.h of the catalyst, and adjusting the H in the reaction system2The reaction was carried out with the flow rate controlled at 50mL/min for 60 hours, and a sample was taken from the collection pot and analyzed by gas chromatography. The diacetone alcohol is subjected to hydrogenation reaction, the conversion rate of the diacetone alcohol is 93.2 percent, and the selectivity of the isohexide is 96.8 percent.
Example 13
Comparative example 8, catalyst stability test was conducted under the same reaction conditions, sampling was conducted at regular intervals, and the reaction data of the continuous test for 500 hours are shown in the following table:
| time (h) | Diacetone alcohol conversion (%) | Isohexane glycol selectivity (%) |
| 60 | 100.0 | 99.3 |
| 100 | 99.7 | 99.5 |
| 150 | 100.0 | 99.2 |
| 200 | 100.0 | 99.3 |
| 250 | 99.8 | 99.7 |
| 300 | 99.6 | 99.8 |
| 400 | 99.8 | 99.2 |
| 500 | 100.0 | 99.6 |
The present invention has been described in detail above, but the present invention is not limited to the specific embodiments described herein.
Claims (7)
1. A method for synthesizing isohexide is characterized in that diacetone alcohol and hydrogen are taken as raw materials to carry out hydrogenation reaction in the presence of a catalyst to prepare the isohexide,
the catalyst is a supported double-component heterogeneous catalyst consisting of active components and a carrier, wherein the first active component of the catalyst is Ni or Cu, the second active component of the catalyst is one of Rh, Au, Re, La, Co, Mn or Ag, and the carrier is one or more than two of active carbon, white carbon black and fumed alumina; the content of the first active component is 0.1-30% of the mass of the catalyst, the content of the second active component is 0.01-10% of the mass of the catalyst, and the balance is a carrier; the supported bi-component heterogeneous catalyst is prepared by the following steps:
(1) mixing the soluble salt of the first main active component and the soluble salt of the second active component with the formula amount, deionized water and the carrier with the formula amount to prepare a mixed solution;
(2) dropwise adding a certain amount of strong ammonia water into the mixed solution prepared in the step (1) until the pH value is 8.5-13.5;
(3) stirring the mixed solution obtained in the step (2) at room temperature for 1-24 hours;
(4) stirring the mixed solution obtained in the step (3) at the temperature of 60-100 ℃ for 2-24 hours;
(5) filtering the mixed solution obtained in the step (4) to obtain a solid product, washing the obtained solid product with deionized water, and then drying the solid product at the temperature of 100 ℃ and 150 ℃ for 2 to 24 hours; then roasting at 200-800 ℃ for 2-24 hours to obtain the supported bi-component heterogeneous catalyst.
2. The method for synthesizing isohexide according to claim 1, wherein the content of the first active component is 5% -25% of the mass of the catalyst, and the content of the second active component is 0.1% -5% of the mass of the catalyst.
3. The method for synthesizing isohexide according to claim 1, wherein the supported bicomponent heterogeneous catalyst is subjected to reduction activation treatment before use, and the conditions of the reduction activation treatment are as follows: the temperature is 120-450 ℃, the pressure is 0.1-2.0 MPa, and the volume space velocity of hydrogen is 500-3000 h-1The treatment time is 1-120 h.
4. The method for synthesizing isohexide according to claim 1, wherein diacetone alcohol and hydrogen are used as raw materials to prepare isohexide by hydrogenation reaction in the presence of a catalyst, and the method comprises the following steps: adding diacetone alcohol raw material into a mixer to mix with hydrogen, and then reacting in a reactor with certain temperature, pressure and catalyst to obtain a product, wherein the reaction conditions are as follows:
the reaction pressure is 0.5-10.0 MPa, the reaction temperature is 30-230 ℃, the molar ratio of hydrogen to diacetone alcohol is 1: 1-150: 1, and the liquid volume space velocity of diacetone alcohol is 0.1-6.0 h-1。
5. The method for synthesizing isohexide according to claim 4, wherein the reaction pressure is 1.5-6.0 MPa, the reaction temperature is 60-120 ℃, the molar ratio of hydrogen to diacetone alcohol is 2: 1-10: 1, and the liquid volume space velocity of diacetone alcohol is 0.1-2.0 h-1。
6. The method for synthesizing isohexide according to claim 4, wherein the reactor is a fixed bed reactor or a slurry bed reactor.
7. The method of claim 4, wherein the reactor is a fixed bed reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010072809.0A CN111153768B (en) | 2020-01-21 | 2020-01-21 | Synthesis method of isohexide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010072809.0A CN111153768B (en) | 2020-01-21 | 2020-01-21 | Synthesis method of isohexide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111153768A true CN111153768A (en) | 2020-05-15 |
| CN111153768B CN111153768B (en) | 2023-06-02 |
Family
ID=70565651
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010072809.0A Active CN111153768B (en) | 2020-01-21 | 2020-01-21 | Synthesis method of isohexide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111153768B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113413890A (en) * | 2021-07-06 | 2021-09-21 | 湖北力拓能源化工装备有限公司 | Porous adsorption catalytic material and preparation method thereof |
| CN113773284A (en) * | 2021-09-16 | 2021-12-10 | 厦门大学 | Method for preparing 2, 5-dihydroxymethyl tetrahydrofuran by hydrogenation of 5-hydroxymethylfurfural |
| CN114369006A (en) * | 2022-01-17 | 2022-04-19 | 湖南长岭石化科技开发有限公司 | Method for preparing isohexide and methyl isobutyl carbinol |
| CN115591551A (en) * | 2022-09-29 | 2023-01-13 | 浙江师范大学（Cn） | Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066608A (en) * | 1991-05-13 | 1992-12-02 | 南开大学 | The catalyzer of hydrogenating reaction of diacetone alcohol |
| CN102329193A (en) * | 2011-07-15 | 2012-01-25 | 荆州市宇鹏科技有限公司 | Process for synthesizing 2-methyl-2,4-pentendiol through hydrogenation reduction of diacetone alcohol |
| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN104549425A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Diacetone alcohol hydrogenation catalyst as well as preparation method and application thereof |
| CN106944065A (en) * | 2017-03-27 | 2017-07-14 | 江苏金聚合金材料有限公司 | The preparation method and application of graphene-supported nickel hydrogenation catalyst |
| CN109806883A (en) * | 2019-01-25 | 2019-05-28 | 浙江师范大学 | Catalyst, with the method and system for use in carrying of catalyst preparation 3- aminopropanol |
-
2020
- 2020-01-21 CN CN202010072809.0A patent/CN111153768B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1066608A (en) * | 1991-05-13 | 1992-12-02 | 南开大学 | The catalyzer of hydrogenating reaction of diacetone alcohol |
| CN102408305A (en) * | 2010-09-21 | 2012-04-11 | 中国石油化工股份有限公司 | Catalytic conversion method of ketone and alcohol |
| CN102329193A (en) * | 2011-07-15 | 2012-01-25 | 荆州市宇鹏科技有限公司 | Process for synthesizing 2-methyl-2,4-pentendiol through hydrogenation reduction of diacetone alcohol |
| CN104549425A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | Diacetone alcohol hydrogenation catalyst as well as preparation method and application thereof |
| CN106944065A (en) * | 2017-03-27 | 2017-07-14 | 江苏金聚合金材料有限公司 | The preparation method and application of graphene-supported nickel hydrogenation catalyst |
| CN109806883A (en) * | 2019-01-25 | 2019-05-28 | 浙江师范大学 | Catalyst, with the method and system for use in carrying of catalyst preparation 3- aminopropanol |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113413890A (en) * | 2021-07-06 | 2021-09-21 | 湖北力拓能源化工装备有限公司 | Porous adsorption catalytic material and preparation method thereof |
| CN113773284A (en) * | 2021-09-16 | 2021-12-10 | 厦门大学 | Method for preparing 2, 5-dihydroxymethyl tetrahydrofuran by hydrogenation of 5-hydroxymethylfurfural |
| CN114369006A (en) * | 2022-01-17 | 2022-04-19 | 湖南长岭石化科技开发有限公司 | Method for preparing isohexide and methyl isobutyl carbinol |
| WO2023134779A1 (en) * | 2022-01-17 | 2023-07-20 | 湖南长炼新材料科技股份公司 | Hydrogenation catalyst and preparation method therefor, and method for preparing isohexanediol and methyl isobutyl carbinol |
| CN114369006B (en) * | 2022-01-17 | 2024-04-12 | 湖南长炼新材料科技股份公司 | Method for preparing isohexide and methyl isobutyl carbinol |
| CN115591551A (en) * | 2022-09-29 | 2023-01-13 | 浙江师范大学（Cn） | Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof |
| CN115591551B (en) * | 2022-09-29 | 2023-10-03 | 浙江师范大学 | Catalyst in continuous flow hydrogenation process of N- (beta-cyanoethyl) -epsilon-caprolactam and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111153768B (en) | 2023-06-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111153768A (en) | Synthetic method of isohexide | |
| CN111233626B (en) | Method for preparing benzhydrol by diphenyl ketone hydrogenation | |
| CN101966460B (en) | Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof | |
| CN113019393B (en) | Platinum nano catalyst, preparation method thereof and method for synthesizing aromatic amine by selective hydrogenation of aromatic nitro compound | |
| CN107497448B (en) | Rhodium/copper alloy nano catalyst and preparation method and application thereof | |
| CN110975882B (en) | Preparation method of catalyst for benzyl alcohol synthesis and catalytic hydrogenation system | |
| CN106582666B (en) | Gamma-valerolactone hydrogenation catalyst, preparation method and the method for being used to prepare 1,4- pentanediol and 2- methyltetrahydrofuran | |
| CN109364962B (en) | Nickel phosphide-based catalyst for selective hydrogenation of acetone and preparation method and application thereof | |
| CN117299165A (en) | Novel synthetic Ni 3 Preparation method and application of catalyst with P and high-efficiency hydrogenation activity | |
| CN110256230A (en) | Efficient catalytic glycerol prepares catalyst of glyceric acid and preparation method thereof under the conditions of a kind of alkali-free | |
| CN109796305B (en) | Method for preparing cyclohexanol by adopting composite catalyst | |
| CN109251126A (en) | A kind of method of cyclohexane oxidation KA oil | |
| CN112642439B (en) | Preparation method of methanation catalyst for low-temperature slurry bed | |
| CN112871159A (en) | Ru nano catalyst and preparation method and application thereof | |
| CN102029155B (en) | Hydrogen producing catalyst | |
| CN113731441B (en) | Cobalt-reduced graphene oxide Co/rGO catalyst and preparation method and application thereof | |
| CN115672377B (en) | Application of nitrogen-doped carbon-supported cobalt catalyst in guaiacol hydrodeoxygenation reaction | |
| CN115715982B (en) | Catalyst suitable for preparing VA and MMP, catalyst preparation method and catalysis method | |
| CN114011421B (en) | Preparation method of hydrogenation catalyst for preparing succinic anhydride from maleic anhydride, and preparation method of succinic anhydride | |
| CN113336624B (en) | Method for selectively hydrogenating phenol on Ni-based catalyst | |
| CN114289051B (en) | Catalyst and method for preparing alicyclic diamine through continuous hydrogenation | |
| CN114192142B (en) | Catalyst for dinonyl phenol hydrogenation and preparation method thereof | |
| CN114950505B (en) | Catalyst for preparing beta-phenethyl alcohol by hydrogenation of styrene oxide, and preparation method and application thereof | |
| CN117586111B (en) | Method for preparing tetrahydrocurcumin through continuous catalytic hydrogenation | |
| CN114433127B (en) | Hydrogenation catalyst, preparation method and application thereof, and method for preparing succinic acid by maleic anhydride hydrogenation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 321001 no.688, Yingbin Avenue, Jinhua City, Zhejiang Province Applicant after: ZHEJIANG NORMAL University Address before: 311231 Xiaoshan campus of Zhejiang Normal University, 1108 Gengwen Road, ningwei Town, Xiaoshan District, Hangzhou City, Zhejiang Province Applicant before: ZHEJIANG NORMAL University |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231120 Address after: 101-1014, 1st Floor, Building 3, No. 103 Beiqing Road, Haidian District, Beijing, 100094 Patentee after: Xiangliu (Beijing) Technology Co.,Ltd. Address before: 321001 no.688, Yingbin Avenue, Jinhua City, Zhejiang Province Patentee before: ZHEJIANG NORMAL University |