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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- WNZQDUSMALZDQF-UHFFFAOYSA-N 2-benzofuran-1(3H)-one Chemical compound C1=CC=C2C(=O)OCC2=C1 WNZQDUSMALZDQF-UHFFFAOYSA-N 0.000 title claims abstract description 102
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 title claims abstract description 46
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000007036 catalytic synthesis reaction Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000000694 effects Effects 0.000 claims abstract description 7
- 239000007810 chemical reaction solvent Substances 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 206010013786 Dry skin Diseases 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000012267 brine Substances 0.000 claims description 7
- 238000005470 impregnation Methods 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 6
- 229910052728 basic metal Inorganic materials 0.000 claims description 6
- 150000003818 basic metals Chemical class 0.000 claims description 6
- 239000010970 precious metal Substances 0.000 claims description 6
- 230000002829 reductive effect Effects 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- VAIVGJYVKZVQAA-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;nickel Chemical compound [Ni].OC(=O)CC(O)(C(O)=O)CC(O)=O VAIVGJYVKZVQAA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000008141 laxative Substances 0.000 claims 2
- 230000002475 laxative effect Effects 0.000 claims 2
- 238000002360 preparation method Methods 0.000 abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- -1 Tio 2 Chemical compound 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 3
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 239000000377 silicon dioxide Substances 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract 1
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 abstract 1
- 239000000969 carrier Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000005506 phthalide group Chemical group 0.000 description 3
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- BOCJQSFSGAZAPQ-UHFFFAOYSA-N 1-chloroanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2Cl BOCJQSFSGAZAPQ-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- DBJUEJCZPKMDPA-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O DBJUEJCZPKMDPA-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003146 anticoagulant agent Substances 0.000 description 1
- 229940127219 anticoagulant drug Drugs 0.000 description 1
- 239000002249 anxiolytic agent Substances 0.000 description 1
- 230000000949 anxiolytic effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N methyl alcohol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Furan Compounds (AREA)
- Catalysts (AREA)
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.
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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 |
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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 |
CN116041294B (en) * | 2023-02-20 | 2024-07-09 | 中国科学院兰州化学物理研究所 | Method for preparing hexahydrophthalide by phthalic anhydride or phthalic acid |
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