CN100439352C - Process for catalytic synthesis of phthalide from phthalic anhydride - Google Patents
Process for catalytic synthesis of phthalide from phthalic anhydride Download PDFInfo
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- CN100439352C CN100439352C CNB2006100523141A CN200610052314A CN100439352C CN 100439352 C CN100439352 C CN 100439352C CN B2006100523141 A CNB2006100523141 A CN B2006100523141A CN 200610052314 A CN200610052314 A CN 200610052314A CN 100439352 C CN100439352 C CN 100439352C
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- phthalide
- phthalic anhydride
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Abstract
The invention relates to a method for catalytic synthesis of phthalide from phthalic anhydride in liquid phase hydrogenation, particularly to a method for catalytic synthesis of phthalide from phthalic anhydride under the action of a load type nickel catalyst. The present invention is characterized in that under the action of the load type nickel catalyst, the phthalide is used as a reaction solvent and selective hydrogenation is carried out through the phthalic anhydride to prepare the phthalide; the ratio by weight of the phthalic anhydride and the phthalide solvent is 1/0.1 to 10; the reacting temperature is 130 to 200 DEG C and the reaction pressure is 1.0 to 5.0MPa. The load type nickel catalyst is a catalyst which loads nickel on SiO2, diatomite, active carbon, Tio 2, ZrO2, Ti02-SiO2, TiO2-Al2O3 or TiO2-ZrO2 carriers; the loading capacity of the nickel is 5 to 50 wt. %. The present invention has the advantages of high activity, stability and selectivity of the load type nickel catalyst, no environment pollution of catalyst preparation, product phthalide directly used as the solvent in reaction, low cost of post product treatment, simple manufacturing process and no environment pollution.
Description
(1) technical field
The present invention relates to a kind of method, particularly the method for catalytic synthesis of phthalide from phthalic anhydride under nickel catalyst carried effect by phthalic anhydride liquid-phase hydrogenatin catalytic synthesis of phthalide.
(2) background technology
Phthalide (adjacent hydroxymethyl phenylformic acid lactone), English name Phthalide, molecular formula C
8H
6O
2, be the intermediate of fine chemicals, medical aspect is used to produce anticoagulant phenyl indan diketone and Somigran, anxiolytic P-3693A and cathartic etc.; The agricultural chemicals aspect is used to produce the sterilant phthalide; Can be used for dyestuff intermediate 1 in addition, 4-dichloroanthraquinone and 1-chloroanthraquinone etc. synthetic.
The synthetic method of phthalide mainly contains phthalic imidine method and phthalic anhydride method.The former is that phthalic imidine and sodium hydroxide effect generate phthalide, and yield is 80%.This method cost of material is than higher, and environmental pollution is more serious in the building-up process.The latter can be divided into chemical reduction method and shortening method again.Chemical reduction method is to be reductive agent with zinc-acetic acid etc., and phthalic anhydride is reduced into phthalide, though this method production technique is simpler, can cause than the serious environmental pollution problem.The phthalic anhydride hydrogenation method is compared with above-mentioned two kinds of methods, has the product yield height, and quality is good, and cost is low, and advantages of environment protection is a up-and-coming phthalide synthetic route.The homogeneous phase noble metal catalyst shows good catalytic in phthalic anhydride liquid-phase hydrogenatin synthesis of phthalide, but the recovery difficulty of catalyzer.The phthalic anhydride hydrogenation reaction also can realize under heterogeneous catalyst effects such as nickel, palladium in organic solvents such as methyl benzoate-methyl alcohol mixed liquor, tetrahydrofuran (THF), but the product postprocessing cost is higher.In recent years, Massonne etc. report with phthalic anhydride hydrogenation products phthalide as reaction solvent, carry out phthalic anhydride hydrogenation reaction system phthalide with Raney Ni as catalyzer, the phthalide yield is 87% (Massonne K, Becker R, Reif W, Neuhauser H, Gieseler A, MundingerK.US 6028204.2000; Massonne K, Becker R, Reif W, Wulff-Doring J.US 6020501.2000).But Raney Ni catalyzer can cause environmental pollution in the preparation, and the problem that exists catalyzer easily to pulverize in the reaction process.
(3) summary of the invention
The synthetic method of the phthalide that the purpose of this invention is to provide that a kind of technology is simple, cost is low, environmental friendliness, transformation efficiency and selectivity is high.
The technical solution used in the present invention is as follows:
A kind of method of catalytic synthesis of phthalide from phthalic anhydride, under nickel catalyst carried effect, with the phthalide is reaction solvent, prepare phthalide by the phthalic anhydride selective hydrogenation, described phthalic anhydride and solvent phthalide mass ratio are 1: 0.1～10,130～200 ℃ of temperature of reaction, reaction pressure 1.0～5.0MPa, described nickel catalyst carried be at SiO with Ni
2, diatomite, gac, TiO
2, ZrO
2, TiO
2-SiO
2, TiO
2-Al
2O
3Or TiO
2-ZrO
2Supported catalyst, the loading of nickel are 5～50wt.%, wherein preferred SiO
2, TiO
2, ZrO
2, TiO
2-SiO
2, TiO
2-Al
2O
3Or TiO
2-ZrO
2Be support of the catalyst.
Described nickel catalyst carried consumption is 0.01～0.2 times of phthalic anhydride quality.
Further, the described nickel catalyst carried oxide compound of one or more elements in precious metal or basic metal, alkaline-earth metal, the rare earth element that can also comprise is as promotor, the content of described promotor is 0～20wt.%, described precious metal is palladium, platinum, ruthenium or rhodium, and described basic metal, alkaline-earth metal or rare earth element are potassium, calcium, magnesium, zirconium, titanium, cerium, lanthanum or samarium.Here the content of promotor is that the connotation of 0～20wt.% is that its content can be infinitely close to 0.
Aforesaid nickel catalyst carried can making by pickling process: with described carrier 400～600 ℃ of roastings 3～8 hours; According to nickel loading calculated value, again with carrier impregnation in the content of nickel by weight of respective amount is 5～50% soluble nickel salt brine solution, the aqueous solution of the preferred nickelous nitrate of soluble nickel salt brine solution, nickelous acetate or citric acid nickel, flooded 2～8 hours down in 15～35 ℃, nickel in the nickel salt aqueous solution will all load on the carrier, then 80～150 ℃ of dryings 2～8 hours, again in 400～800 ℃ of following roastings 2～8 hours, at last 300～700 ℃ of reduction 1～10 hour down.If contain auxiliary agent in nickel catalyst carried, then earlier with the carrier impregnation after the roasting in the soluble salt aqueous solution of 0～20% the precious metal by weight that calculates respective amount according to the auxiliary agent loading or basic metal, alkaline-earth metal, rare earth element, 15～35 ℃ flooded 2～8 hours, 80～150 ℃ of dryings 2～8 hours are again in 400～800 ℃ of following roastings 2～8 hours; And then to impregnated in the content of nickel by weight that calculates respective amount according to the nickel loading be in 5～50% the soluble nickel salt brine solution, 15～35 ℃ flooded 2～8 hours, 80～150 ℃ of dryings 2～8 hours, again in 400～800 ℃ of following roastings 2～8 hours, last 300～700 ℃ were reduced 1～10 hour down, and described reduction can be carried out in hydrogen atmosphere or hydrogen nitrogen mixture atmosphere.
Concrete, the method of described catalytic synthesis of phthalide from phthalic anhydride, step is as follows: according to phthalic anhydride: phthalide: nickel catalyst carried mass ratio is 1: 0.1～10: 0.01～0.2 to add autoclave successively, air in the logical hydrogen exchange still also keeps the pressure of 1.0～3.2MPa, intensification also maintains the temperature at 150～180 ℃, turn on agitator reaction 1～8 hour, reaction finishes back separating reaction liquid and nickel catalyst carried, reaction solution carries out alkali cleaning, filtration, is described phthalide after the gained filter cake washing.
The present invention compared with prior art, its advantage is embodied in:
1. employed nickel catalyst carried activity and stability are high, and selectivity is good; Preparation of catalysts is free from environmental pollution;
The reaction directly with the product phthalide as solvent, the aftertreatment cost of product is low, technology is simple, and is environmentally friendly.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1:
The immersion process for preparing catalyzer:
1) pre-treatment of carrier is with SiO
2Carrier was 400～600 ℃ of roastings 3～5 hours;
2) load active component, with step 1) pretreated carrier be 20 ℃ of 10% nickel nitrate aqueous solutions dipping 6 hours down with nickel content by weight, dry down at 110 ℃ then, 500 ℃ of roastings 4 hours, the last catalyzer that in hydrogen atmosphere, can obtain phthalic anhydride hydrogenation synthesis of phthalide after 3 hours in reduction under 500 ℃.
With 700 milligrams of Ni/SiO
2Catalyzer adds 100 milliliters of autoclaves, again 17.8 gram phthalic anhydrides, 41.5 gram solvent phthalides is added autoclave, 150 ℃ of temperature of reaction, and reaction hydrogen pressure 3.0MPa, in 4 hours reaction times, the transformation efficiency of phthalic anhydride is 85.5%, the yield of phthalide is 69.7%.
Embodiment 2:
Catalyst preparation process is with embodiment 1, and difference is that catalyzer is with TiO
2-ZrO
2Be carrier, nickel content is 15wt%.With 700 milligrams of Ni/TiO
2-ZrO
2Catalyzer adds 100 milliliters of autoclaves, 170 ℃ of temperature of reaction, and reaction hydrogen pressure 3.2MPa, other condition is with embodiment 1, and in 5 hours reaction times, the transformation efficiency of phthalic anhydride is 93.3%, and the yield of phthalide is 88.7%.
Embodiment 3:
Catalyst preparation process is with embodiment 2, and difference is that catalyzer is with TiO
2-SiO
2Be carrier.With 700 milligrams of Ni/TiO
2-SiO
2Catalyzer adds 100 milliliters of autoclaves, 180 ℃ of temperature of reaction, and reaction hydrogen pressure 3.0MPa, other condition is with embodiment 1, and in 6 hours reaction times, the transformation efficiency of phthalic anhydride is 98.5%, and the yield of phthalide is 91.4%.
Embodiment 4:
Catalyst preparation process is with embodiment 2, and difference is carrier impregnation in the nickelous acetate aqueous solution.With 20.1 gram phthalic anhydrides, 40.2 gram solvent phthalides, 800 milligrams of Ni/TiO
2-ZrO
2Catalyzer adds 100 milliliters of autoclaves, 180 ℃ of temperature of reaction, and reaction hydrogen pressure 3.0MPa, in 4 hours reaction times, the transformation efficiency of phthalic anhydride is 79.8%, the yield of phthalide is 77.8%.
Embodiment 5:
Catalyst preparation process is with embodiment 4, and difference is carrier impregnation in the citric acid nickel aqueous solution.Phthalic anhydride catalytic hydrogenation reaction condition is with embodiment 4, and in 4 hours reaction times, the transformation efficiency of phthalic anhydride is 97.1%, and the yield of phthalide is 92.9%.
Embodiment 6:
Catalyst preparation process is with embodiment 5, and difference is that catalyzer is with TiO
2-Al
2O
3Be carrier, carrier impregnation is in nickel nitrate aqueous solution.Phthalic anhydride catalytic hydrogenation reaction condition is with embodiment 4, and in 4 hours reaction times, the transformation efficiency of phthalic anhydride is 69.5%, and the yield of phthalide is 67.9%.
Embodiment 7:
With TiO
2-ZrO
2Carrier is 500 ℃ of roastings 5 hours, impregnated in content by weight then and is in the nitrate aqueous solution of 3% rare-earth elements of lanthanum, in 15～35 ℃ of dippings 5 hours down, then 80～150 ℃ of dryings 5 hours, again in 400～800 ℃ of following roastings 4 hours; And then to impregnated in nickel content by weight be in 10% the nickelous nitrate salt brine solution, in 15～35 ℃ of following dippings 4 hours, then 80～150 ℃ of dryings 3 hours, again in 400～800 ℃ of following roastings 5 hours, reduced 3 hours down at 300～700 ℃ at last, obtain Ni/La
2O
3-TiO
2-ZrO
2Catalyzer.
With 30 gram phthalic anhydrides, 30 gram solvent phthalides, 1.5 gram Ni/La
2O
3-TiO
2-ZrO
2Catalyzer adds 100 milliliters of autoclaves, 170 ℃ of temperature of reaction, and reaction hydrogen pressure 2.8MPa, in 4 hours reaction times, the phthalic anhydride transformation efficiency is 92.6%, the phthalide yield is 88.9%.
Claims (8)
1. the method for a catalytic synthesis of phthalide from phthalic anhydride, it is characterized in that described method is under nickel catalyst carried effect, with the phthalide is reaction solvent, prepare phthalide by the phthalic anhydride selective hydrogenation, described phthalic anhydride and solvent phthalide mass ratio are 1: 0.1～10,130～200 ℃ of temperature of reaction, reaction pressure 1.0～5.0MPa, described nickel catalyst carried be at TiO with Ni
2--SiO
2, TiO
2-Al
2O
3Or TiO
2-ZrO
2Supported catalyst, the loading of nickel are 5～50wt.%.
2. the method for catalytic synthesis of phthalide from phthalic anhydride as claimed in claim 1 is characterized in that described nickel catalyst carried consumption is 0.01～0.2 times of phthalic anhydride quality.
3. the method for catalytic synthesis of phthalide from phthalic anhydride as claimed in claim 2, it is characterized in that the described nickel catalyst carried oxide compound of one or more elements in precious metal or basic metal, alkaline-earth metal, the rare earth element that also comprises is as promotor, the content of described promotor is 0～20wt.%, described precious metal is palladium, platinum, ruthenium or rhodium, described basic metal, alkaline-earth metal or rare earth element are potassium, calcium, magnesium, zirconium, titanium, cerium, lanthanum or samarium, and the content of described promotor is that the implication of 0～20wt.% is that the content of promotor can be infinitely close to 0.
4. the method for catalytic synthesis of phthalide from phthalic anhydride as claimed in claim 1 is characterized in that described nickel catalyst carriedly made by laxative remedy: with described carrier 400～600 ℃ of roastings 3～8 hours; Again according to nickel loading calculated value, with carrier impregnation in the content of nickel by weight of respective amount is 5～50% soluble nickel salt brine solution, flooded 2～8 hours down in 15～35 ℃, then 80～150 ℃ of dryings 2～8 hours, in 400～800 ℃ of following roastings 2～8 hours, reduced 1～10 hour down at 300～700 ℃ at last again.
5. the method for catalytic synthesis of phthalide from phthalic anhydride as claimed in claim 3, it is characterized in that described nickel catalyst carriedly make by laxative remedy: with described carrier 400～600 ℃ of roastings 3～8 hours, according to calculated value, is in the soluble salt aqueous solution of 0～20% precious metal or basic metal, alkaline-earth metal, rare earth element with carrier impregnation in the content by weight of respective amount, flooded 2～8 hours down in 15～35 ℃, then 80～150 ℃ of dryings 2～8 hours, again in 400～800 ℃ of following roastings 2～8 hours; And then to impregnated in the content of nickel by weight that calculates respective amount according to the nickel loading be in 5～50% the soluble nickel salt brine solution, flooded 2～8 hours down in 15～35 ℃, then 80～150 ℃ of dryings 2～8 hours, in 400～800 ℃ of following roastings 2～8 hours, reduced 1～10 hour down at 300～700 ℃ at last again.
6. as the method for one of claim 4 or 5 described catalytic synthesis of phthalide from phthalic anhydride, it is characterized in that described soluble nickel salt brine solution is the aqueous solution of nickelous nitrate, nickelous acetate or citric acid nickel.
7. the method for catalytic synthesis of phthalide from phthalic anhydride as claimed in claim 6 is characterized in that described reduction is to reduce 1～10 hour under 300～700 ℃ in hydrogen atmosphere or hydrogen nitrogen mixture atmosphere.
8. the method for catalytic synthesis of phthalide from phthalic anhydride as claimed in claim 1, the step that it is characterized in that described method is as follows: according to phthalic anhydride: phthalide: nickel catalyst carried mass ratio is 1: 0.1～10: 0.01～0.2 to add autoclave successively, air in the logical hydrogen exchange still also keeps the pressure of 1.0～3.2MPa, intensification also remains on 150～180 ℃, turn on agitator reaction 1～8 hour, reaction finishes back separating reaction liquid and nickel catalyst carried, reaction solution carries out alkali cleaning, filtration, is described phthalide after the gained filter cake washing.
Priority Applications (1)
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|---|---|---|---|
| CNB2006100523141A CN100439352C (en) | 2006-07-05 | 2006-07-05 | Process for catalytic synthesis of phthalide from phthalic anhydride |
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|---|---|---|---|
| CNB2006100523141A CN100439352C (en) | 2006-07-05 | 2006-07-05 | Process for catalytic synthesis of phthalide from phthalic anhydride |
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|---|---|
| CN1884272A CN1884272A (en) | 2006-12-27 |
| CN100439352C true CN100439352C (en) | 2008-12-03 |
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| CN103055883A (en) * | 2012-12-28 | 2013-04-24 | 浙江大学 | Supported nickel-based catalyst and its preparation method and use |
| CN103433043B (en) * | 2013-08-28 | 2015-04-08 | 大连理工大学 | High-selectivity catalyst for preparing phthalide by hydrogenation of phthalic anhydride |
| CN107353271A (en) * | 2016-05-10 | 2017-11-17 | 中国石油化工股份有限公司 | The method for purifying the method for phthalide and phthalide being prepared by phthalic anhydride |
| CN108126702A (en) * | 2017-12-27 | 2018-06-08 | 上海迅凯新材料科技有限公司 | A kind of load-type nickel series catalysts and its preparation method and application |
| CN110240578A (en) * | 2018-03-08 | 2019-09-17 | 华东师范大学 | A kind of plus hydrogen prepares the method for tetrahydrofurfuryl alcohol and nickel catalyst carried |
| CN110724046A (en) * | 2018-07-17 | 2020-01-24 | 唐山旭阳化工有限公司 | Method for preparing o-methylbenzoic acid and phthalide from phthalic anhydride |
| CN110773175A (en) * | 2019-11-07 | 2020-02-11 | 江苏美思德化学股份有限公司 | Supported metal catalyst, preparation method and application thereof, and synthesis process of N-methylmorpholine |
| CN114716397B (en) * | 2022-03-10 | 2022-09-09 | 大连理工大学 | Preparation method for preparing phthalide by normal pressure hydrogenation of phthalic anhydride |
| CN114797817B (en) * | 2022-03-14 | 2024-05-03 | 西安凯立新材料股份有限公司 | Catalyst for preparing m-xylylenediamine by continuous catalytic hydrogenation and preparation method and application thereof |
| CN115504951B (en) * | 2022-10-21 | 2024-02-13 | 大连理工大学 | Method for preparing hexahydrophthalide by hydrogenating hexahydrophthalic anhydride |
| CN116041294A (en) * | 2023-02-20 | 2023-05-02 | 中国科学院兰州化学物理研究所 | Method for preparing hexahydrophthalide by phthalic anhydride or phthalic acid |
Citations (4)
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-
2006
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Patent Citations (4)
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|---|---|---|---|---|
| US4528385A (en) * | 1982-01-18 | 1985-07-09 | Dynamit Nobel Ag | Method of preparing phthalide |
| US4973713A (en) * | 1989-11-28 | 1990-11-27 | E. I. Du Pont De Nemours And Company | Catalytic hydrogenation of carboxylic anhydrides to esters or lactones |
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