CN114315495B - Method for synthesizing methylcyclopentadiene from 2, 5-hexanedione - Google Patents
Method for synthesizing methylcyclopentadiene from 2, 5-hexanedione Download PDFInfo
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- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 title claims abstract description 124
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 44
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 54
- 239000001257 hydrogen Substances 0.000 claims description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims description 53
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 238000005470 impregnation Methods 0.000 claims description 11
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 10
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 claims description 4
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 2
- 238000007598 dipping method Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 10
- 238000005882 aldol condensation reaction Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 description 10
- CHCCBPDEADMNCI-UHFFFAOYSA-N 3-methylcyclopenten-2-one Natural products CC1=CC(=O)CC1 CHCCBPDEADMNCI-UHFFFAOYSA-N 0.000 description 7
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000011987 methylation Effects 0.000 description 2
- 238000007069 methylation reaction Methods 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 238000005336 cracking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- OONRXMHENUMURA-UHFFFAOYSA-N manganese;1-methylcyclopenta-1,3-diene Chemical compound [Mn].CC1=CC=CC1 OONRXMHENUMURA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000002760 rocket fuel Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000002641 tar oil Substances 0.000 description 1
- CMQCNTNASCDNGR-UHFFFAOYSA-N toluene;hydrate Chemical compound O.CC1=CC=CC=C1 CMQCNTNASCDNGR-UHFFFAOYSA-N 0.000 description 1
Classifications
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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)
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Abstract
The invention relates to a method for synthesizing methylcyclopentadiene from 2, 5-hexanedione, which takes 2, 5-hexanedione as a raw material and synthesizes a methylcyclopentadiene target product through aldol condensation serial hydrodeoxygenation reaction in a fixed bed continuous reactor under the action of a supported metal oxide A/X type catalyst. The invention has simple process route, is environment-friendly, has simple catalyst preparation and provides a brand new effective way for synthesizing the methylcyclopentadiene from the 2, 5-hexanedione.
Description
Technical Field
The invention belongs to the technical field of chemical preparation, and particularly relates to a method for synthesizing methylcyclopentadiene from 2, 5-hexanedione.
Background
The methylcyclopentadiene not only can be used for synthesizing high-energy rocket fuel, but also is a high-end fine chemical raw material with wide application, and can be used for synthesizing high-added value products such as a gasoline antiknock agent Methylcyclopentadiene Manganese Tricarbonyl (MMT), an epoxy resin curing agent, a dye additive, a special adhesive, a special spice and the like. There are two main methods for the production of MCPD in industry: a method for preparing the high-temp cracking tar oil from petroleum includes such steps as distilling to separate C 6 The components are polymerized, distilled under reduced pressure, depolymerized and rectified for a plurality of times to prepare the MCPD; another is the methylation of cyclopentadiene to produce MCPD. However, the productivity of MCPD, whether produced by separation or methylation synthesis, is very limited and far from meeting the application requirements of various fields. Therefore, it is of great significance to find a green renewable synthetic process route for producing methylcyclopentadiene using bulk chemicals as raw materials.
In recent years, with increasing attention to environmental and energy problems, synthesis of high value-added chemicals from carbon dioxide neutral, renewable biomass resources has been widely paid to countries around the world. For example, catalytic hydrogenolysis of cellulose can yield 2, 5-hexanedione (appl. Catalyst. A,2015, 504, 664-671). Using 2, 5-hexanedione as raw material, under the action of basic catalyst Mg-Al-O, using water-toluene mixed solvent to make aldol condensation reaction so as to obtain 3-methyl-2-cyclopentene-1-one (MCP), and making MCP implement catalyst Pt/NbOPO 4 Under the action of (a), hydrodeoxygenation can be carried out to obtain the product, i.e. methylcyclopentane, which has a low carbon number and loses the ability to further polymerize (Green chem.,2015, 17, 2393-2397). MCP is used as a raw material, methyl cyclopentadiene can be obtained through one-step hydrodeoxygenation, the highest methyl cyclopentadiene selectivity can reach 80 percent, but MCP is used as the raw material, and the raw material yield is limited and the price is highProblems.
Disclosure of Invention
Aiming at the technical problems, the invention provides a method for synthesizing methylcyclopentadiene by one step of 2, 5-hexanedione, which is a novel, simple and efficient synthetic method for preparing methylcyclopentadiene by one step of 2, 5-hexanedione by converting 2, 5-hexanedione into target product methylcyclopentadiene in a fixed bed continuous reactor under the action of a supported metal oxide A/X type catalyst.
The invention is realized by the following technical scheme:
2, 5-hexanedione is used as a raw material, and the methylcyclopentadiene is obtained in one step through aldol condensation-hydrodeoxygenation reaction under the action of a supported metal oxide A/X type catalyst; wherein, the component A is metal oxide, the component X is carrier, and the reaction path of the above reaction is shown in figure 3.
The chemical structural formula of the raw material 2, 5-hexanedione and the target product methylcyclopentadiene is shown in table 1.
Based on the above scheme, preferably, the above reaction is performed in a fixed bed continuous reactor under the following reaction conditions: the reaction temperature is 300-600 ℃ (preferably 320-550 ℃, more preferably 350-500 ℃), the hydrogen pressure is 0.0001-1MPa (preferably 0.0001-0.9MPa, more preferably 0.0001-0.8 MPa), the molar ratio of hydrogen to 2, 5-hexanedione is 5-400:1 (preferably 10-350:1, more preferably 20-300:1), and the mass space velocity of 2, 5-hexanedione is 0.01-10h -1 (preferably 0.05-8 h) -1 More preferably 0.1 to 5 hours -1 )。
Based on the above, preferably, the supported metal oxide A/X type catalyst employs Al 2 O 3 、SiO 2 、ZrO 2 、MgO、CaO、Nb 2 O 5 、CeO 2 Or one or more of ZnO as a carrier component X, fe 3 O 4 、V 2 O 5 、WO 3 、CuO、MoO 3 Or Co 3 O 4 One or more of (a) is a metal oxide component a, wherein the mass fraction of the metal oxide component a is 1 to 85% (preferably 2 to 75%, more preferably 3 to 65%), and the balance is a support component X.
Based on the above scheme, preferably, the supported metal oxide A/X type catalyst is prepared by an impregnation method or a precipitation deposition method, and is subjected to a reduction treatment in hydrogen gas before use.
Based on the above-described scheme, preferably, the reduction treatment conditions of the supported metal oxide a/X type catalyst are: the hydrogen pressure is 0.001-2.0MPa (preferably 0.005-1.5MPa, more preferably 0.01-1 MPa), the hydrogen flow rate is 2-300mL/min (preferably 5-250mL/min, more preferably 10-200 mL/min), the reduction temperature is 200-600 ℃ (preferably 250-550 ℃, more preferably 300-500 ℃), and the reduction time is 0.5-12h (preferably 0.7-10h, more preferably 1-8 h).
Based on the above scheme, preferably, the supported metal oxide A/X type catalyst is prepared by an impregnation method by controlling the composition of the catalyst metal oxide component A. The specific preparation process is as follows: the carrier component X is pretreated for 1 to 24 hours (preferably for 1.5 to 20 hours, more preferably for 2 to 15 hours) at 100 to 700 ℃ (preferably for 200 to 650 ℃, more preferably for 250 to 600 ℃) before impregnation, the impregnation liquid is an aqueous solution of a soluble salt of the metal oxide component A, the pretreated carrier component X is impregnated in the impregnation liquid by one or more steps, after impregnation for 1 to 36 hours (preferably for 2 to 30 hours, more preferably for 3 to 24 hours), dried for 4 to 48 hours at 50 to 150 ℃, and then baked for 0.1 to 10 hours (preferably for 0.5 to 8 hours, more preferably for 1 to 6 hours) at 200 to 800 ℃ (preferably for 300 to 750 ℃, more preferably for 350 to 700 ℃) and the mass fraction of the metal oxide component A is controlled within the range of 1 to 85% (preferably for 2 to 75%, more preferably for 3 to 65%).
Based on the above scheme, preferably, the supported metal oxide A/X type catalyst can also be prepared by a deposition precipitation method by controlling the composition of the catalyst metal oxide component A. The specific preparation process is as follows: the aqueous solution of the soluble salt of the metal oxide component A is divided into two parts by mass, B and C, the carrier component X is added to B, the precipitant is added to C, then C is slowly added to B at 30-110 ℃ (preferably 40-100 ℃, more preferably 50-90 ℃), and after stirring for 1-20h (preferably 2-15h, more preferably 3-12 h) at 30-110 ℃ (preferably 40-100 ℃, more preferably 50-90 ℃), the mixture is dried in an oven at 100-200 ℃ for 4-48h, and then baked at 300-800 ℃ (preferably 350-750 ℃, more preferably 400-700 ℃) for 0.5-10h (preferably 1-8h, more preferably 1-6 h), and the mass fraction of the metal oxide component A is controlled within the range of 1-85% (preferably 2-75%, more preferably 3-65%). The precipitant is one or more of LiOH, naOH, KOH, ammonia water and urea, and the molar ratio of the addition of the precipitant to the soluble salt of the component A in the component C is 1-5:1, preferably 1-4:1; more preferably 1-3:1.
Advantageous effects
The method disclosed by the invention has few operation steps, can directly obtain the methylcyclopentadiene from the 2, 5-hexanedione through aldol condensation serial hydrodeoxygenation reaction in one step, is a green and simple new synthetic route, has the advantages of simple preparation method, mild reaction conditions, good stability and regeneration performance, generally higher conversion rate of the 2, 5-hexanedione, excellent selectivity of the methylcyclopentadiene, and can be used for practical industrial production.
The invention adopts a fixed bed continuous flow reactor, can convert 2, 5-hexanedione into methyl cyclopentadiene in one step under the action of the catalyst, and has the advantages of simple process route, high operability, low energy consumption, simple catalyst preparation and small environmental pollution.
According to the invention, the source raw material 2, 5-hexanedione for synthesizing MCP is used as a substrate for the first time, and methyl cyclopentadiene with high added value can be directly synthesized in one step through aldol condensation serial hydrodeoxygenation reaction in a fixed bed continuous reactor under the condition of no solvent, and the reaction selectivity is higher than that of the previous report. Up to the present, there is no report on synthesizing methylcyclopentadiene by using 2, 5-hexanedione as a raw material and performing aldol condensation and hydrodeoxygenation reaction in one step.
Drawings
FIG. 1 is a gas chromatogram of the product of synthesizing methylcyclopentadiene from 2, 5-hexanedione in example 5.
FIG. 2 is a mass spectrum contrast chart of the target product methylcyclopentadiene.
FIG. 3 shows the reaction path of the present invention.
Detailed Description
The technical scheme of the present invention is described in further detail below with reference to specific embodiments, but the scope of the present invention is not limited to these embodiments.
Example 1
(1) Supported metal oxide A/X catalyst Co 3 O 4 /Al 2 O 3 Is prepared from the following steps: weighing 4g of Al pretreated for 15h at 250 DEG C 2 O 3 The mixture was immersed in an aqueous solution containing 2.91g of cobalt nitrate in an equal volume for 12 hours, dried at 60℃for 48 hours, and then calcined at 500℃for 4 hours. Co produced 3 O 4 /Al 2 O 3 Metal oxide Co in catalyst 3 O 4 The content of (C) is 16.7wt%, and the carrier Al 2 O 3 The content of (C) was 83.3% by weight.
(2) Co as described above 3 O 4 /Al 2 O 3 1g of catalyst is filled in a fixed bed continuous reactor, then the catalyst is reduced for 1h under the conditions of hydrogen pressure of 0.2MPa, hydrogen flow rate of 60mL/min and reduction temperature of 450 ℃, then the bed temperature of the fixed bed continuous reactor is kept at 450 ℃, the reaction pressure is controlled to be 0.02MPa, and the hourly space velocity of 2, 5-hexanedione is controlled to be 0.8h -1 The molar ratio of hydrogen to 2, 5-hexanedione was 50:1, the conversion of 2, 5-hexanedione was 98% and the selectivity to methylcyclopentadiene was 88%.
Example 2
(1) Supported metal oxide A/X catalyst Fe 3 O 4 /CeO 2 Is prepared from the following steps: 100 g of aqueous solution containing 5g of ferric nitrate is prepared and is divided into two parts B and C by equal mass, and 8g of carrier CeO is added into the B 2 Adding 8g of urea into C, slowly adding C into B in a water bath at 50 ℃, stirring at 80 ℃ for 5 hours, drying at 120 ℃ for 12 hours, and roasting at 600 ℃ for 2 hours. The metal oxide component Fe in the prepared catalyst 3 O 4 The content of (C) is 14.2wt%, and the carrier is CeO 2 The content of (C) was 85.8wt%.
(2) The Fe is mixed with 3 O 4 /CeO 2 1g of catalyst is filled in a fixed bed continuous reactor, and then the catalyst is heated at a hydrogen pressure of 1MPa and a hydrogen flow rate of 160mL/min at a reduction temperatureReducing for 4h at 400 ℃, then keeping the bed temperature of the fixed bed continuous reactor at 400 ℃, controlling the reaction pressure to be 0.5MPa and the hourly space velocity of 2, 5-hexanedione to be 1.2h -1 The molar ratio of hydrogen to 2, 5-hexanedione was 100:1, the conversion of 2, 5-hexanedione was 95% and the selectivity to methylcyclopentadiene was 84%.
Example 3
(1) Supported metal oxide A/X catalyst WO 3 /ZrO 2 Is prepared from the following steps: 5g of ZrO after pretreatment at 600℃for 2 hours were weighed out 2 The mixture was immersed in an aqueous solution containing 3.3g of sodium tungstate for 5 hours, dried at 120℃for 12 hours, then baked at 700℃for 2 hours, and then pressed into tablets. WO prepared 3 /ZrO 2 Metal oxide component WO in the catalyst 3 The content of (C) was 31.7% by weight, and the carrier ZrO 2 The content of (C) was 68.3% by weight.
(2) WO as described above 3 /ZrO 2 1g of catalyst is filled in a fixed bed continuous reactor, then reduced for 1h under the conditions of hydrogen pressure of 0.8MPa, hydrogen flow of 180mL/min and reduction temperature of 500 ℃, and then the reaction temperature of 450 ℃ is controlled, the reaction pressure of 0.05MPa and the hourly space velocity of 2, 5-hexanedione of 0.9h -1 The molar ratio of hydrogen to 2, 5-hexanedione was 200:1, the conversion of 2, 5-hexanedione was 100%, and the selectivity to methylcyclopentadiene was 87%.
Example 4
(1) Supported metal oxide A/X catalyst CuO/Nb 2 O 5 Is prepared from the following steps: 100 g of aqueous solution containing 4g of copper nitrate is prepared and is divided into two parts B and C by equal mass, 5g of carrier Nb is added into the B 2 O 5 Adding 10g of urea into C, slowly adding C into B in a water bath at 50 ℃, stirring at 80 ℃ for 2 hours, drying at 120 ℃ for 40 hours, roasting at 500 ℃ for 3 hours, and tabletting and forming. The prepared catalyst contains 5wt% of CuO as metal oxide component and Nb as carrier 2 O 5 The content of (2) was 95% by weight.
(2) The CuO/Nb is prepared from 2 O 5 1g of catalyst is filled in a fixed bed continuous reactor, and then the catalyst is added under the conditions of hydrogen pressure of 0.01MPa, hydrogen flow rate of 80mL/min and reduction temperature of 400 DEG CThe reaction pressure is 0.1MPa, and the hourly space velocity of 2, 5-hexanedione is 0.6h after the original 3h, and then the bed temperature of the fixed bed continuous reactor is controlled at 400 DEG C -1 The molar ratio of the hydrogen to the 2, 5-hexanedione is 100:1, the conversion of the 2, 5-hexanedione is 100%, and the selectivity of the methylcyclopentadiene is 86%.
Example 5
(1) Supported metal oxide A/X catalyst V 2 O 5 /SiO 2 Is prepared from the following steps: 100 g of aqueous solution containing 2.3 g of ammonium metavanadate is prepared and is equally divided into two parts B and C, and 3g of carrier SiO is added into the B 2 Adding 10g of urea into C, slowly adding C into B in a water bath at 50 ℃, stirring at 80 ℃ for 2 hours, drying at 120 ℃ for 40 hours, roasting at 500 ℃ for 3 hours, and tabletting and forming. Metal oxide component V in the catalyst prepared 2 O 5 The content of (C) is 32.6wt%, and the carrier SiO 2 The content of (C) was 67.4% by weight.
(2) The V is set up above 2 O 5 /SiO 2 1g of catalyst is filled in a fixed bed continuous reactor, then the catalyst is reduced for 1h under the conditions of hydrogen pressure of 0.01MPa, hydrogen flow rate of 150mL/min and reduction temperature of 600 ℃, then the bed temperature of the fixed bed continuous reactor is controlled at 300 ℃, the reaction pressure of 0.6MPa and the hourly space velocity of 2, 5-hexanedione of 0.6h -1 The molar ratio of hydrogen to 2, 5-hexanedione was 150:1, the conversion of 2, 5-hexanedione was 96%, and the selectivity to methylcyclopentadiene was 85%.
Example 6
(1) Supported metal oxide A/X catalyst MoO 3 Preparation of ZnO: 5g of ZnO pretreated at 600 ℃ for 1 hour is weighed, immersed in an aqueous solution containing 1.1g of ammonium heptamolybdate in an equal volume, dried at 120 ℃ for 12 hours after being immersed for 12 hours, then baked at 600 ℃ for 1 hour, and then pressed into tablets for molding. MoO prepared 3 Metal oxide component MoO in ZnO catalyst 3 The content of (2) was 15wt% and the content of ZnO as a carrier was 85wt%.
(2) The MoO is prepared 3 1g of ZnO catalyst is filled in a fixed bed continuous reactor, then reduced for 2 hours under the conditions of hydrogen pressure of 0.01MPa, hydrogen space velocity of 90mL/min and 400 ℃, and then the fixed bed is usedThe bed temperature of the continuous reactor was maintained at 400℃and the reaction pressure was 0.01MPa, and the hourly space velocity of 2, 5-hexanedione was 1.1h -1 The molar ratio of hydrogen to 2, 5-hexanedione was 50:1, the conversion of 2, 5-hexanedione was 100%, and the selectivity to methylcyclopentadiene was 92%.
Example 7
(1) Supported metal oxide A/X catalyst MoO 3 Preparation of CaO: 5g of ZnO pretreated at 600 ℃ for 1 hour is weighed, immersed in an aqueous solution containing 1.1g of ammonium heptamolybdate in an equal volume, dried at 120 ℃ for 12 hours after being immersed for 12 hours, then baked at 600 ℃ for 1 hour, and then pressed into tablets for molding. MoO prepared 3 MoO as metal oxide component in CaO catalyst 3 The content of (2) was 15wt% and the content of CaO as a carrier was 85wt%.
(2) The MoO is prepared 3 1g of CaO catalyst is filled in a fixed bed continuous reactor, then reduced for 2 hours under the conditions of hydrogen pressure of 0.01MPa, hydrogen space velocity of 90mL/min and 400 ℃, then the bed temperature of the fixed bed continuous reactor is kept at 400 ℃, the reaction pressure of 0.01MPa and the hourly space velocity of 2, 5-hexanedione of 0.9 hours -1 The molar ratio of hydrogen to 2, 5-hexanedione was 50:1, the conversion of 2, 5-hexanedione was 100%, and the selectivity to methylcyclopentadiene was 84%.
Example 8
(1) Supported metal oxide A/X catalyst MoO 3 Preparation of MgO: 5g of MgO, pretreated at 600 ℃ for 1 hour, is weighed, immersed in an aqueous solution containing 1.1g of ammonium heptamolybdate in an equal volume, dried at 120 ℃ for 12 hours after being immersed for 12 hours, then baked at 600 ℃ for 1 hour, and then pressed into tablets for molding. MoO prepared 3 Metal oxide component MoO in ZnO catalyst 3 The content of MgO in the composition was 15wt% and the content of MgO in the support was 85wt%.
(2) The MoO is prepared 3 1g of ZnO catalyst is filled in a fixed bed continuous reactor, then reduced for 2 hours under the conditions of hydrogen pressure of 0.01MPa, hydrogen space velocity of 90mL/min and 400 ℃, then the bed temperature of the fixed bed continuous reactor is kept at 400 ℃, the reaction pressure of 0.01MPa and the hourly space velocity of 2, 5-hexanedione of 0.9 hours -1 The molar ratio of the hydrogen to the 2, 5-hexanedione is 50:1,the conversion of 2, 5-hexanedione was 100% and the selectivity of methylcyclopentadiene was 88%.
Example 9
(1) Supported metal oxide A/X catalyst Fe 3 O 4 -MoO 3 Preparation of MgO: 10g of MgO pretreated at 500 ℃ for 3 hours is weighed, immersed in an aqueous solution containing 1g of ferric nitrate and 2g of ammonium heptamolybdate in an equal volume, dried at 100 ℃ for 20 hours after 24 hours, then baked at 600 ℃ for 2 hours, and then pressed into tablets for molding. Fe prepared 3 O 4 -MoO 3 Metal oxide component Fe in MgO catalyst 3 O 4 The content of (2) was 1.6wt%, the metal oxide component MoO 3 13.8wt% and 84.6wt% of MgO as a carrier.
(2) The Fe is mixed with 3 O 4 -MoO 3 1.5g of MgO catalyst is filled in a fixed bed continuous reactor, then reduced for 3 hours under the conditions of hydrogen pressure of 0.1MPa, hydrogen of 110mL/min and reduction temperature of 450 ℃, then the bed temperature of the fixed bed continuous reactor is reduced to the reaction temperature of 380 ℃, the reaction pressure of 0.1MPa and the hourly space velocity of 2, 5-hexanedione of 0.9 hours -1 The molar ratio of hydrogen to 2, 5-hexanedione was 150:1, the conversion of 2, 5-hexanedione was 100%, and the selectivity to methylcyclopentadiene was 82%.
Example 10
(1) Supported metal oxide A/X catalyst WO 3 /ZnO-ZrO 2 Is prepared from the following steps: weighing 3.5g ZnO pretreated for 12 hours at 300 ℃ and 3.5g ZrO pretreated for 2 hours at 400 DEG 2 Uniformly mixing, soaking the mixture in an aqueous solution containing 3.3g of sodium tungstate for 6 hours, drying at 80 ℃ for 24 hours, roasting at 650 ℃ for 3 hours, and tabletting and forming. WO prepared 3 /ZnO-ZrO 2 Metal oxide component WO in the catalyst 3 The content of (C) was 24.9wt%, and the carriers ZnO and ZrO were used 2 The content of (C) was 75.1% by weight.
(2) WO as described above 3 /ZnO-ZrO 2 1.5g of catalyst is filled in a fixed bed continuous reactor, then reduced for 2 hours at the temperature of 550 ℃ under the hydrogen pressure of 0.5MPa and the hydrogen flow rate of 110mL/min, and then the bed of the fixed bed continuous reactorThe layer temperature was kept at 450℃and the reaction pressure was 0.1MPa and the hourly space velocity of 2, 5-hexanedione was 0.6h -1 The molar ratio of hydrogen to 2, 5-hexanedione was 200:1, the conversion of 2, 5-hexanedione was 100%, and the selectivity to methylcyclopentadiene was 94%.
Example 11
(1) Supported metal oxide A/X catalyst V 2 O 5 /SiO 2 -Al 2 O 3 Is prepared from the following steps: weighing 5g of SiO pretreated for 3 hours at 500 DEG C 2 And 2g of Al pretreated at 600 ℃ for 3 hours 2 O 3 Uniformly mixing, soaking the mixture in an aqueous solution containing 5g of ammonium metavanadate in an equal volume, drying at 100 ℃ for 24 hours after soaking for 3 hours, roasting at 500 ℃ for 3 hours, and tabletting and forming. V prepared 2 O 5 /SiO 2 -Al 2 O 3 Metal oxide component V in catalyst 2 O 5 The content of (C) is 36wt%, carrier SiO 2 And Al 2 O 3 The content of (2) was 64% by weight.
(2) The V is set up above 2 O 5 /SiO 2 -Al 2 O 3 1.5g of catalyst is filled in a fixed bed continuous reactor, then the catalyst is reduced for 1h under the conditions of hydrogen pressure of 1MPa, hydrogen flow of 190mL/min and reduction temperature of 450 ℃, then the bed temperature of the fixed bed continuous reactor is kept at 450 ℃, the reaction pressure of 0.5MPa and the hourly space velocity of 2, 5-hexanedione of 0.9h -1 The molar ratio of hydrogen to 2, 5-hexanedione was 250:1, the conversion of 2, 5-hexanedione was 94% and the selectivity to methylcyclopentadiene was 89%.
Example 12
(1) Supported metal oxide A/X catalyst Co 3 O 4 -WO 3 /Nb 2 O 5 Is prepared from the following steps: weighing 3g of Nb which is pretreated for 2 hours at 300 DEG C 2 O 5 Immersing the mixture in an equal volume of aqueous solution containing 3.3g of sodium tungstate for 8 hours, and drying the mixture at 120 ℃ for 12 hours; the catalyst obtained was then immersed in an equal volume of an aqueous solution containing 0.6g of cobalt nitrate for 8 hours and dried at 120℃for 12 hours. Finally, roasting for 2 hours at 600 ℃, and tabletting and forming. Co produced 3 O 4 -WO 3 /Nb 2 O 5 Metal oxide component Co in catalyst 3 O 4 The content of (2.5 wt.%) metal oxide component WO 3 The content of (C) is 39.8wt%, and the carrier Nb 2 O 5 The content of (2) was 57.7% by weight.
(2) Co as described above 3 O 4 -WO 3 /Nb 2 O 5 2g of catalyst is filled in a fixed bed continuous reactor, then the catalyst is reduced for 2 hours at the temperature of 400 ℃ under the conditions of hydrogen pressure of 0.2MPa, hydrogen flow rate of 150mL/min and reduction temperature of 400 ℃, then the bed temperature of the fixed bed continuous reactor is kept at 400 ℃, the reaction pressure of 0.01MPa and the hourly space velocity of 2, 5-hexanedione of 1.1 hours -1 The molar ratio of hydrogen to 2, 5-hexanedione was 150:1, the conversion of 2, 5-hexanedione was 95% and the selectivity to methylcyclopentadiene was 87%.
The results of the experiments described above for examples 1-10 are shown in Table 2.
TABLE 2 hydrodeoxygenation of methylcyclopentadiene from 2, 5-hexanedione
Examples 13 to 29
In example 10 WO 3 /ZnO-ZrO 2 As a catalyst, 2g of the catalyst was packed in a fixed bed continuous reactor, 2, 5-hexanedione was used as a substrate, and then reduced at a hydrogen pressure of 0.05MPa and a reduction temperature of 400 ℃ for 1 hour, and the reaction was carried out at a certain molar ratio of hydrogen to 2, 5-hexanedione, a reaction temperature, a reaction pressure and an hourly space velocity, and the reaction results were shown in table 3.
Table 3 WO 3 /ZnO-ZrO 2 Catalytic synthesis of methylcyclopentadiene from 2, 5-hexanedione hydrodeoxygenation
Claims (5)
1. A method for synthesizing methylcyclopentadiene, the method comprising the steps of:
2, 5-hexanedione is used as a raw material, and the methyl cyclopentadiene is obtained through aldol condensation-hydrodeoxygenation reaction in one step under the action of an A/X type catalyst, and the reaction is carried out in a fixed bed continuous reactor; the reaction temperature is 300-600 ℃, the hydrogen pressure is 0.0001-1MPa, the molar ratio of hydrogen to raw materials is 5-400:1, and the mass airspeed of the raw materials is 0.01-10h -1 ；
Wherein, the component A is metal oxide, and the component X is carrier;
the mass fraction of the component A is 1-85%, and the component A is selected from Fe 3 O 4 、V 2 O 5 、WO 3 、CuO、MoO 3 Or Co 3 O 4 One or more of the following;
the component X is selected from Al 2 O 3 、SiO 2 、ZrO 2 、MgO、CaO、Nb 2 O 5 、CeO 2 Or ZnO;
the catalyst is prepared by adopting an impregnation method or a deposition precipitation method, and is subjected to reduction treatment in hydrogen before use, wherein the reduction conditions are as follows: the hydrogen pressure is 0.005-1.5MPa, the hydrogen flow rate is 5-250mL/min, the reduction temperature is 250-550 ℃, and the reduction time is 0.7-10 h;
the impregnation method comprises the following steps:
step one, pretreatment of a carrier: pretreating the component X for 1-24 hours at 100-700 ℃ before soaking;
step two, active component impregnation: taking an aqueous solution of soluble salt of the component A as an impregnating solution, placing the pretreated component X into the impregnating solution through one or more steps, impregnating 1-36 and h, drying 4-48 and h at 50-150 ℃, and roasting for 0.1-10h at 200-800 ℃ to obtain the A/X type catalyst;
the deposition precipitation method comprises the following steps:
the method comprises the steps of equally dividing an aqueous solution of soluble salt of a component A into two parts of B and C, adding a component X into the B, adding a precipitant into the C, adding the C into the B at 30-110 ℃, stirring for 1-20h at 30-110 ℃, drying for 4-48h in a baking oven at 100-200 ℃, and roasting for 0.5-10h at 300-800 ℃ to obtain the A/X type catalyst;
the precipitant is one or more of LiOH, naOH, KOH, ammonia water and urea, and the molar ratio of the addition amount of the precipitant to the soluble salt of the component A in the component C is 1-5:1.
2. The method according to claim 1, wherein the mass fraction of component a is 2-75%; the reaction temperature is 320-550 ℃, the hydrogen pressure is 0.0001-0.9MPa, and the mass airspeed of the raw materials is 0.05-9 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of the hydrogen to the raw materials is 10-350:1.
3. The method according to claim 2, wherein the mass fraction of component a is 3-65%; the reaction temperature is 350-500 ℃, the hydrogen pressure is 0.0001-0.8MPa, and the mass airspeed of the raw materials is 0.1-8 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The molar ratio of the hydrogen to the raw materials is 20-300:1.
4. A method according to claim 1, characterized in that:
the reduction conditions are as follows: hydrogen pressure is 0.01-1MPa, hydrogen flow rate is 10-200mL/min, reduction temperature is 300-500 ℃, and reduction time is 1-8 h;
in the impregnation method:
step one, the pretreatment temperature of the component X is 200-650 ℃ and the pretreatment time is 1.5-20h;
step two, the dipping time is 2-30h, the roasting temperature is 300-750 ℃ and the roasting time is 0.5-8h;
in the deposition precipitation method: c adding B at 40-100deg.C, and stirring at 40-100deg.C for 2-15 hr; the roasting temperature is 350-750 ℃ and the roasting time is 1-8 h; the molar ratio of the adding amount of the precipitant to the soluble salt of the component A in the component C is 1-4:1.
5. The method of claim 4, wherein:
in the impregnation method:
step one, the pretreatment temperature of the component X is 250-600 ℃ and the pretreatment time is 2-15h;
step two, soaking for 3-24h, roasting at 350-700 ℃ for 1-6h;
in the deposition precipitation method: adding B into C at 50-90deg.C, and stirring at 50-90deg.C for 3-12 hr; the roasting temperature is 400-700 ℃ and the roasting time is 1-6h; the molar ratio of the adding amount of the precipitant to the soluble salt of the component A in the component C is 1-3:1.
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