CN101875602A - Heterogeneous catalysis method for synthesizing isophorone from acetone - Google Patents
Heterogeneous catalysis method for synthesizing isophorone from acetone Download PDFInfo
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- CN101875602A CN101875602A CN2009100831305A CN200910083130A CN101875602A CN 101875602 A CN101875602 A CN 101875602A CN 2009100831305 A CN2009100831305 A CN 2009100831305A CN 200910083130 A CN200910083130 A CN 200910083130A CN 101875602 A CN101875602 A CN 101875602A
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 140
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 21
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 238000007210 heterogeneous catalysis Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims abstract description 4
- 238000012360 testing method Methods 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 3
- 239000010935 stainless steel Substances 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 229910003023 Mg-Al Inorganic materials 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000002638 heterogeneous catalyst Substances 0.000 claims description 4
- 229910001051 Magnalium Inorganic materials 0.000 claims description 2
- 229910020068 MgAl Inorganic materials 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 27
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000011777 magnesium Substances 0.000 abstract description 4
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- 229910026161 MgAl2O4 Inorganic materials 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 229910052596 spinel Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 32
- 239000008367 deionised water Substances 0.000 description 21
- 229910021641 deionized water Inorganic materials 0.000 description 21
- 238000005070 sampling Methods 0.000 description 16
- 238000001816 cooling Methods 0.000 description 11
- 239000012065 filter cake Substances 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229960001545 hydrotalcite Drugs 0.000 description 3
- 229910001701 hydrotalcite Inorganic materials 0.000 description 3
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 235000011470 Adenanthera pavonina Nutrition 0.000 description 1
- 241000428378 Lopa Species 0.000 description 1
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a heterogeneous catalysis method for synthesizing isophorone by acetone, which takes acetone as a raw material and magnesium aluminum composite oxide as a catalyst to synthesize isophorone by catalysis; the magnesium-aluminum composite oxide is prepared from MgO and Al2O3And MgAl2O4The composition has Mg/Al molar ratio of 0.3-3 and specific surface area of 80-150m2Per g, pore volume of 0.2-0.3cm3(ii)/g; carrying out synthetic reaction by using a fixed bed reactor, adding 20ml of 20-40 mesh catalyst into a stainless steel reactor with the inner diameter of 10mm, heating the mixture to the reaction temperature from room temperature at the speed of 10 ℃/min after passing an air-tight test, and injecting an analytically pure acetone raw material into the reactor through a double-plunger pump and a preheater; the reaction temperature is 220-290 ℃; the reaction pressure is normal pressure; the space velocity of the acetone liquid is 0.1-1.0h-1The selectivity reaches 94.5%, the conversion rate reaches 44.8%, and the stability reaches 1000 hours.
Description
Technical field
The present invention relates to green, clean catalysis technical field, specifically refer to a kind of heterogeneous catalytic method, wherein use magnesium-aluminium composite oxide to make catalyzer, under the reaction conditions of gentleness, carry out the condensation reaction of acetone gas-solid heterogeneous catalyst by synthesis of isophorone from acetone.
Background technology
Isophorone is as one of deep processed product of acetone, and development is very fast in developed countries such as American and Britain, moral, days.Along with the chemical industry especially fast development of synthetic resins industry, the demand of isophorone also increases fast.Beginning of the nineties late 1980s, much more external family was newly-built or extended the isophorone production equipment, the production of isophorone at present mainly concentrates on western developed country and area with consumption, main manufacturer has U.S. Rohm and Haas Company (US) Independenec Mall West, Philadelphia, Pennsy Lvania 1, U.S. combinating carbide company, BP chemical company, Germany dimension Bagong department, Huels AG, Japanese contest Lopa Nationality company, sumitomo chemical company etc., overall throughput is 100,000 t/a.And China does not still have producer's suitability for industrialized production isophorone at present, and reagent enterprise of a few family produced in small quantities is only arranged, as Shanghai experiment reagent company limited, and the Long Huagongshijichang of Chengdu section etc.; Units such as Shanghai solvent factory, Ji Hua company of PetroChina Company Limited. carry out excessive quantity research work, once have pilot plant on a small scale.But the domestic production industrialization still belongs to blank.
Mainly be divided into two kinds by the comparatively sophisticated technology of synthesis of isophorone from acetone: mesityl oxide method and acetone condensation method.Wherein industrialized synthetic method is based on acetone condensation method.The method of condensation of acetone synthesis of isophorone can be divided into two kinds again by contact condition: a kind of is pressurization liquid phase condensation method in basic solution, and another kind is the heterogeneous catalyst condensation method of solid catalyst.The isophorone total recovery that the liquid phase condensation method obtains is about 60～70%, acetone conversion about 6～10%.It is simple, easy to operate that this method has a catalyzer, isophorone yield advantages of higher, be specially adapted to suitability for industrialized production, but shortcoming can not be ignored, promptly reactor is a high-tension apparatus, internal structure is complicated, acetone conversion is not high, and production cost is higher, contains a large amount of potassium hydroxide in the waste liquid, not only etching apparatus, separation and aftertreatment are difficult, and the distillation tower operating process is also wayward.In addition, this technology produces high dense strong basicity organic liquid waste, waste water, causes environmental pollution.And development environment close friend's catalyzer and relevant catalysis synthesizing technology thereof more and more cause people's attention.Chinese scholars is carried out primary study to acetone gas-solid phase preparing isophorone using condensation technology in recent years.This method has the acetone conversion height, and catalyzer easily prepares, and reactor is advantages such as fixed bed, easy amplification.In solid catalyst, the magnalium system receives increasing concern because of its suitable acid-basicity position.Dang Mingyan etc. have prepared magnesium-aluminium composite oxide catalyzer, the highlyest can obtain 19.0% acetone conversion and 47.4% isophorone selectivity.J.I.Cosimo has investigated the influence of Mg-Al hydrotalcite to the condensation reaction of acetone gas-solid phase, the Mg-Al hydrotalcite of finding MgO and roasting to isophorone, mesityl oxide and isomers selectivity thereof near 100%.The author points out that isophorone is to generate under the effect of surface hydroxyl, the magnesium aluminum-hydrotalcite of high Al content is the suitable catalyzer that condensation of acetone prepares isophorone.C.Flego etc. have studied the aldol reaction of going up acetone at a series of acidic molecular sieves (comprising aperture, hollow, large pore zeolite and micropore, mesoporous amorphous aluminum silicide).The transformation efficiency that the result shows acetone is relevant with B acid acid position on the molecular sieve and increase along with the increase of the sour bit density of molecular sieve.Aristech company has synthesized a kind of Mg-Al composite oxide and has made catalyzer, found that, on this catalyzer, acetone conversion is up to 32.5%, and the isophorone selectivity reaches 74.8%.On the basis of this catalyzer, the said firm has developed a kind of new catalyzer again, adds diatomite, moulding then, drying, roasting in magnesium/aluminium composite anion clay.Evaluation result shows that on this catalyzer, acetone conversion can reach 27.9%, and isophorone adds the mesityl oxide selectivity and reaches 87%, and 1200 hours non-inactivations of catalyzer continuous operation.Though the heterogeneous condensation method of acetone gas-solid has many advantages, from the result of study of present stage, there are shortcomings such as preparation technology's relative complex, cost height, life-span weak point, regeneration difficulty and isophorone selectivity are low in the catalyzer of being developed.So the key of this Technology is that the development activity is high, selectivity is high, the life-span is long, the simple novel solid catalyzer of preparation.
Summary of the invention:
The object of the invention is to use magnesium-aluminium composite oxide to make catalyzer, at low temperature, normal pressure and do not add under the mild conditions of any solvent, realizes that efficient, highly selective and high stability ground are by acetone gas-solid heterogeneous catalyst condensation prepared isophorone.
Reaction expression of the present invention is:
The present invention relates to a kind of heterogeneous catalytic method by synthesis of isophorone from acetone.It is characterized in that using acetone as reactant, select for use a kind of Mg-Al composite oxide as catalyzer, is that 220-290 ℃, reaction pressure are that normal pressure, acetone liquid feeding air speed are 0.1-1.0h in temperature of reaction
-1Condition under carry out.This method reaction conditions gentleness, technical security, the green low toxicity of technological process, simultaneously, the catalyst system therefor preparation is simple, and cost is low, selectivity height, good stability.
According to above-mentioned described synthetic method, the Mg-Al composite oxide catalyzer is by MgO, Al
2O
3And MgAl
2O
4Form specific surface area of catalyst 80-150m
2/ g, pore volume are 0.2-0.3cm
3/ g.
Concrete preparation method is as follows:
1. get magnesium nitrate and aluminum nitrate is dissolved in distilled water, control Mg/Al mol ratio is 0.3-3, is mixed with magnesium nitrate, the aluminum nitrate mixing salt solution A of 0.1-2 volumetric molar concentration.
2. keep A solution at 38-42 ℃, and under agitation in A solution, dropwise add NH
3.H
2O to pH is worth to 8-11.
3. drip NH
3.H
2After O finishes, A solution was warming up to 60-100 ℃ of aging 3-12 hour.
4. leave standstill cooling 1-6h after-filtration.
5. be 7.0-10.0 with deionized water wash filter cake to filtrate pH value.
6. dried overnight in 80-120 ℃ of baking oven, under air atmosphere 350-700 ℃ roasting 2-7 hour.
According to above-mentioned described synthetic method, by synthesis of isophorone from acetone reaction, at normal pressure, temperature of reaction 220-290 ℃, acetone solution air speed 0.1-1.0h
-1Operational condition under carry out.Adopt fixed-bed reactor to carry out this building-up reactions, dress 20ml, 20-40 order catalyzer add in the stainless steel reactor of internal diameter 10mm, after gas-tightness test is qualified, with the speed of 10 ℃/min from the room temperature temperature programming to temperature of reaction, again with analytical pure acetone raw material by doubleplunger pump in the preheater injecting reactor.Products therefrom cools off through 0 ℃ cold-trap, collects.Product analysis carries out chromatographic column adopting PEG-20000 capillary column on the 2010 gas chromatograph fid detectors of Tianjin, island.
According to above-mentioned described synthetic method, by the synthesis of isophorone from acetone heterogeneous catalytic reaction, acetone conversion reaches as high as 44.8%, and the isophorone selectivity reaches as high as 95.4%.This catalyzer also has good stability, and the life-span can reach more than 1000 hours.
The present invention compared with prior art has following advantage:
1. reaction conditions gentleness, technical security, the green low toxicity of technological process.
2. method for preparing catalyst is simple, and is with low cost.
3. catalyzer has highly selective, high stability and higher activity.
Description of drawings
The test of Fig. 1 Mg-Al composite oxide catalyst stability, reaction conditions: 0.1MPa, 290 ℃, 1.0h
-1
Embodiment
Embodiment 1
23.08 gram magnesium nitrate hexahydrates and 56.27 grams, nine water aluminum nitrates are dissolved in the 2000ml deionized water, under 38 ℃, dropwise add ammoniacal liquor to pH be 8.5.70 ℃ of following constant temperature wore out 12 hours, left standstill cooling 1 hour.Filter and be 7.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of following dried overnight made catalyzer in 7 hours in 350 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 220 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 20.3%, and the isophorone selectivity is 86.5%.
Embodiment 2
Preparation of Catalyst is with embodiment 1.The evaluating catalyst condition is: normal pressure, 250 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 25.2%, and the isophorone selectivity is 90.0%.
Embodiment 3
Preparation of Catalyst is with embodiment 1.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 34.5%, and the isophorone selectivity is 90.2%.
Embodiment 4
23.08 gram magnesium nitrate hexahydrates and 56.27 grams, nine water aluminum nitrates are dissolved in the 2000ml deionized water, under 38 ℃, dropwise add ammoniacal liquor to pH be 9.0.70 ℃ of following constant temperature wore out 8 hours, left standstill cooling 4 hours.Filter and be 8.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of following dried overnight made catalyzer in 6 hours in 400 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 34.8%, and the isophorone selectivity is 89.5%.
Embodiment 5
Preparation of Catalyst is with embodiment 4.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.23ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 38.0%, and the isophorone selectivity is 91.4%.
Embodiment 6
Preparation of Catalyst is with embodiment 4.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.13ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 42.3%, and the isophorone selectivity is 90.0%.
Embodiment 7
Preparation of Catalyst is with embodiment 4.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.03ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 44.8%, and the isophorone selectivity is 90.5%.
Embodiment 8
269.26 gram magnesium nitrate hexahydrates and 393.90 grams, nine water aluminum nitrates are dissolved in the 1000ml deionized water, under 40 ℃, dropwise add ammoniacal liquor to pH be 9.0.70 ℃ of following constant temperature wore out 8 hours, left standstill cooling 4 hours.Filter and be 8.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of following dried overnight made catalyzer in 6 hours in 400 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 36.3%, and the isophorone selectivity is 88.4%.
Embodiment 9
269.26 gram magnesium nitrate hexahydrates and 393.90 grams, nine water aluminum nitrates are dissolved in the 1000ml deionized water, under 40 ℃, dropwise add ammoniacal liquor to pH be 9.0.100 ℃ of following constant temperature wore out 3 hours, left standstill cooling 6 hours.Filter and be 8.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of following dried overnight made catalyzer in 3 hours in 600 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 36.9%, and the isophorone selectivity is 91.2%.
Embodiment 10
269.26 gram magnesium nitrate hexahydrates and 393.90 grams, nine water aluminum nitrates are dissolved in the 1000ml deionized water, under 40 ℃, dropwise add ammoniacal liquor to pH be 10.0.60 ℃ of following constant temperature wore out 8 hours, left standstill cooling 4 hours.Filter and be 9.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of following dried overnight made catalyzer in 6 hours in 400 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 35.8%, and the isophorone selectivity is 95.4%.
Embodiment 11
269.26 gram magnesium nitrate hexahydrates and 393.90 grams, nine water aluminum nitrates are dissolved in the 1000ml deionized water, under 41 ℃, dropwise add ammoniacal liquor to pH be 10.5.60 ℃ of following constant temperature wore out 6 hours, left standstill cooling 4 hours.Filter and be 9.0 with deionized water drip washing filter cake to filtrate pH value.120 ℃ of following dried overnight made catalyzer in 2 hours in 700 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 39.6%, and the isophorone selectivity is 89.1%.
Embodiment 12
269.26 gram magnesium nitrate hexahydrates and 393.90 grams, nine water aluminum nitrates are dissolved in the 1000ml deionized water, under 40 ℃, dropwise add ammoniacal liquor to pH be 11.0.60 ℃ of following constant temperature wore out 6 hours, left standstill cooling 4 hours.Filter and be 10.0 with deionized water drip washing filter cake to filtrate pH value.120 ℃ of following dried overnight made catalyzer in 3 hours in 600 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 29.1%, and the isophorone selectivity is 88.5%.
Embodiment 13
23.08 gram magnesium nitrate hexahydrates and 13.5 grams, nine water aluminum nitrates are dissolved in the 400ml deionized water, under 42 ℃, dropwise add ammoniacal liquor to pH be 11.0.60 ℃ of following constant temperature wore out 6 hours, left standstill cooling 4 hours.Filter and be 10.0 with deionized water drip washing filter cake to filtrate pH value.120 ℃ of following dried overnight made catalyzer in 6 hours in 400 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 22.3%, and the isophorone selectivity is 80.9%.
Embodiment 14
23.08 gram magnesium nitrate hexahydrates and 13.5 grams, nine water aluminum nitrates are dissolved in the 400ml deionized water, under 40 ℃, dropwise add ammoniacal liquor to pH be 10.0.60 ℃ of following constant temperature wore out 6 hours, left standstill cooling 4 hours.Filter and be 9.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of following dried overnight made catalyzer in 6 hours in 400 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 26.3%, and the isophorone selectivity is 88.6%.
Embodiment 15
23.08 gram magnesium nitrate hexahydrates and 13.5 grams, nine water aluminum nitrates are dissolved in the 400ml deionized water, under 42 ℃, dropwise add ammoniacal liquor to pH be 11.0.60 ℃ of following constant temperature wore out 3 hours, left standstill cooling 4 hours.Filter and be 7.0 with deionized water drip washing filter cake to filtrate pH value.80 ℃ of following dried overnight made catalyzer in 3 hours in 600 ℃ of roastings under the air atmosphere.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and after reaction was carried out 24 hours, sampling was analyzed, and acetone conversion is 19.2%, and the isophorone selectivity is 80.0%.
Embodiment 16
This example is a research object with embodiment 10 catalyzer, has carried out stability test.The evaluating catalyst condition is: normal pressure, 290 ℃, acetone feed amount are 0.33ml/mim, and sampling analysis is spaced apart 24 hours, always lasts more than 1000 hours.The results are shown in Figure 1.
From Fig. 1 as seen, on this catalyzer, acetone conversion maintains about 31%, and the isophorone selectivity maintains about 92%, and reaction was gone through 1000 hours, and catalyzer is inactivation not.
Claims (1)
1. the heterogeneous catalytic method by synthesis of isophorone from acetone is characterized in that: do raw material with acetone, make catalyzer with Mg-Al composite oxide, through the heterogeneous catalyst synthesis of isophorone;
Mg-Al composite oxide is by MgO, Al
2O
3And MgAl
2O
4Form, the magnalium mol ratio is 0.3-3, and specific surface is 80-150m
2/ g, pore volume are 0.2-0.3cm
3/ g;
Adopt fixed-bed reactor to carry out building-up reactions, 20ml, 20-40 order catalyzer are added in the stainless steel reactor of internal diameter 10mm, after gas-tightness test is qualified, speed with 10 ℃/min is warming up to temperature of reaction from room temperature, again with analytical pure acetone raw material by doubleplunger pump in the preheater injecting reactor;
Temperature of reaction is 220-290 ℃;
Reaction pressure is a normal pressure;
Acetone liquid air speed is 0.1-1.0h
-1
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976910A (en) * | 2011-09-05 | 2013-03-20 | 张锦碧 | Environment-friendly and simple preparation method for synthesizing isophorone from acetone |
| CN105126801A (en) * | 2015-08-28 | 2015-12-09 | 厦门大学 | Catalyst used for synthesizing isophorone and preparation method thereof |
| CN105268422A (en) * | 2014-07-11 | 2016-01-27 | 中国石油化工股份有限公司 | Preparation method of isophorone catalyst |
| CN104549371B (en) * | 2013-10-22 | 2016-11-23 | 中国石油化工股份有限公司 | Catalyst of preparing isophorone using condensation of acetone and preparation method thereof |
| CN106831385A (en) * | 2015-12-03 | 2017-06-13 | 中国石油化工股份有限公司 | The method that acetone prepares isophorone |
| CN111097397A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for synthesizing mesityl oxide and isophorone |
| CN115038522A (en) * | 2020-10-27 | 2022-09-09 | 锦湖石油化学株式会社 | Molded catalyst, method for producing same, and method for producing cyclic ketone using same |
| CN116514643A (en) * | 2023-04-28 | 2023-08-01 | 山东新和成维生素有限公司 | Production method and production system of beta-isophorone |
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| 王芳珠等: "以镁铝水滑石为前驱体制备复合氧化物催化丙酮气相缩合反应", 《无机化学学报》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102976910A (en) * | 2011-09-05 | 2013-03-20 | 张锦碧 | Environment-friendly and simple preparation method for synthesizing isophorone from acetone |
| CN104549371B (en) * | 2013-10-22 | 2016-11-23 | 中国石油化工股份有限公司 | Catalyst of preparing isophorone using condensation of acetone and preparation method thereof |
| CN105268422A (en) * | 2014-07-11 | 2016-01-27 | 中国石油化工股份有限公司 | Preparation method of isophorone catalyst |
| CN105126801A (en) * | 2015-08-28 | 2015-12-09 | 厦门大学 | Catalyst used for synthesizing isophorone and preparation method thereof |
| CN106831385A (en) * | 2015-12-03 | 2017-06-13 | 中国石油化工股份有限公司 | The method that acetone prepares isophorone |
| CN106831385B (en) * | 2015-12-03 | 2020-06-09 | 中国石油化工股份有限公司 | Method for preparing isophorone from acetone |
| CN111097397A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Method for synthesizing mesityl oxide and isophorone |
| CN115038522A (en) * | 2020-10-27 | 2022-09-09 | 锦湖石油化学株式会社 | Molded catalyst, method for producing same, and method for producing cyclic ketone using same |
| CN116514643A (en) * | 2023-04-28 | 2023-08-01 | 山东新和成维生素有限公司 | Production method and production system of beta-isophorone |
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