CN106967365A - A kind of method that abjection combined chloride prepares low-chlorine bleach lac - Google Patents
A kind of method that abjection combined chloride prepares low-chlorine bleach lac Download PDFInfo
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- CN106967365A CN106967365A CN201710275715.1A CN201710275715A CN106967365A CN 106967365 A CN106967365 A CN 106967365A CN 201710275715 A CN201710275715 A CN 201710275715A CN 106967365 A CN106967365 A CN 106967365A
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- 239000000460 chlorine Substances 0.000 title claims abstract description 33
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 33
- 239000007844 bleaching agent Substances 0.000 title claims abstract description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 57
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 57
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 57
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 56
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 229920001800 Shellac Polymers 0.000 claims abstract description 36
- 239000004208 shellac Substances 0.000 claims abstract description 36
- ZLGIYFNHBLSMPS-ATJNOEHPSA-N shellac Chemical compound OCCCCCC(O)C(O)CCCCCCCC(O)=O.C1C23[C@H](C(O)=O)CCC2[C@](C)(CO)[C@@H]1C(C(O)=O)=C[C@@H]3O ZLGIYFNHBLSMPS-ATJNOEHPSA-N 0.000 claims abstract description 36
- 229940113147 shellac Drugs 0.000 claims abstract description 36
- 235000013874 shellac Nutrition 0.000 claims abstract description 36
- 238000004061 bleaching Methods 0.000 claims abstract description 35
- 239000000203 mixture Substances 0.000 claims abstract description 13
- 239000000706 filtrate Substances 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 8
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 49
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- 238000001035 drying Methods 0.000 claims description 23
- 238000000120 microwave digestion Methods 0.000 claims description 21
- 230000001590 oxidative effect Effects 0.000 claims description 21
- 229910052763 palladium Inorganic materials 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000012065 filter cake Substances 0.000 claims description 14
- 230000036571 hydration Effects 0.000 claims description 14
- 238000006703 hydration reaction Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 206010013786 Dry skin Diseases 0.000 claims description 9
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 241000245032 Trillium Species 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 235000013305 food Nutrition 0.000 abstract description 7
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 3
- 238000010494 dissociation reaction Methods 0.000 abstract description 3
- 230000005593 dissociations Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002702 enteric coating Substances 0.000 description 1
- 238000009505 enteric coating Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000012176 shellac wax Substances 0.000 description 1
- 238000009898 sodium hypochlorite bleaching Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/02—Purification
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of method that abjection combined chloride prepares low-chlorine bleach lac, belong to technical field of fine.Bleaching shellac is added in ethanol first and obtains bleaching shellac ethanol solution；Pd Ni/ γ Al are added into bleaching shellac ethanol solution2O3‑SiO2Bimetallic catalyst, then passes to hydrogen, under the conditions of microwave irradiation in reaction temperature be room temperature to 70 DEG C reaction 30 ~ 120min, after reaction terminates, bimetallic catalyst and filtrate are filtrated to get, vacuum drying obtains low-chlorine bleach lac, wherein Pd Ni/ γ Al after filtrate goes out ethanol through vacuum distillation2O3‑SiO2Pd weight/mass percentage compositions are that 0.5% ~ 2.0%, Ni weight/mass percentage compositions are 0.5% ~ 5.0%, γ Al in bimetallic catalyst2O3With SiO2Mass ratio be 1 ~ 3:1.The present invention utilizes Pd Ni/ γ Al2O3‑SiO2Combined chloride in the absorption hydrogen and the characteristic of catalytic hydrogenation reaction of complex carrier bimetallic catalyst, catalytic dissociation bleaching shellac, which is prepared, can be used for the low-chlorine bleach lac of food and pharmaceutical industry.
Description
Technical field
The present invention relates to a kind of method that abjection combined chloride prepares low-chlorine bleach lac, belong to technical field of fine.
Background technology
Lac is also known as shellac, is a kind of natural products resource of regeneration, by lac resin, shellac wax and lac pigment group
Into the product for extracting the pigment after pigment and wax with sodium hypochlorite destruction remnants is referred to as bleaching shellac, is commonly used for pharmaceutical preparation
Enteric coating material, edible packing material, in the fresh-keeping of industry, the moisturizing operation such as fruit, candy.
However, the existing bleaching shellac chlorinity by sodium hypochlorite bleaching technique productions is all in more than 2.0% (wt%).Lead
Cause to combine the reason for chlorinity is high in bleaching shellac, can occur chlorination with resin because of sodium hypochlorite in bleaching shellac production process
Addition, forms combined chloride on molecular resin.Combined chloride is during the storage process of bleaching shellac and transport with the shape of hydrogen chloride
Formula is dissociated, and the polymerization with intramolecular between catalyst action, acceleration molecular resin is played to lac resin molecule aggregation, drift is ultimately resulted in
Trillium glue loses solubility property.Up to now, poor storage performance is still the deadly defect of bleaching shellac, therefore each production firm
The general shelf life of products for all only promising to undertake six months or so.Combined chloride in bleaching shellac reduces the shelf-life of product, also limits
Its use in food and pharmacy industry is made, the bleaching shellac requirement chlorinity that food and pharmacy industry are used is less than 1.0%
(wt%).The polymerization process of combined chloride meeting catalytic resin, makes product shelf characteric be deteriorated, storage period is usually no more than half a year, to production
The transports of product, sale and using bringing very big inconvenience.Although in addition, bleaching shellac can be used for food and pharmacy industry, combining
The presence of chlorine can produce harmful effect to the security of food, limit the utilization in these industries.
The content of the invention
For there is combined chloride in bleaching shellac, and combined chloride to the negative effect of properties of product and purposes the problem of, this
Invention provides a kind of method that abjection combined chloride prepares low-chlorine bleach lac.The present invention utilizes Pd-Ni/ γ-Al2O3-SiO2It is compound
Combined chloride in the absorption hydrogen and the characteristic of catalytic hydrogenation reaction of carrier bimetallic catalyst, catalytic dissociation bleaching shellac is prepared into
To the low-chlorine bleach lac of food and pharmaceutical industry can be used for.The present invention is achieved through the following technical solutions.
A kind of method that abjection combined chloride prepares low-chlorine bleach lac, it is comprised the following steps that：
（1）First by bleaching shellac according to solid-to-liquid ratio be 100:300 ~ 600g/mL is added to concentration to be floated in 95wt% ethanol
Trillium glue ethanol solution；
（2）To step（1）In obtained bleaching shellac ethanol solution according to solid-to-liquid ratio be 1.0 ~ 5.0:300 ~ 600g/mL is added
Pd-Ni/γ-Al2O3-SiO2Bimetallic catalyst, then passes to hydrogen, under the conditions of microwave irradiation in reaction temperature be room temperature
To 70 DEG C of 30 ~ 120min of reaction, after reaction terminates, bimetallic catalyst and filtrate are filtrated to get, filtrate goes out second through vacuum distillation
Vacuum drying obtains low-chlorine bleach lac, wherein Pd-Ni/ γ-Al after alcohol2O3-SiO2Pd mass percentage contains in bimetallic catalyst
It is 0.5% ~ 5.0%, γ-Al to measure as 0.5% ~ 2.0%, Ni weight/mass percentage compositions2O3With SiO2Mass ratio be 1 ~ 3:1.
The step（2）The hydrogen that middle hydrogen flow rate is 50 ~ 100mL/min, purity is 99.99%
The step（2）It in pressure be that -0.08MPa, temperature are 30 ~ 60min of drying at 40 DEG C that middle vacuum drying condition, which is,.
The step（2）Middle Pd-Ni/ γ-Al2O3-SiO2The preparation method of bimetallic catalyst：
The carrier of bimetallic catalyst is A and B, and wherein A is γ type nano-aluminium oxides；Material B is that granularity is less than 0.841mm
Silica, to analyze pure palladium bichloride and analyze pure hydration nickel sulfate as raw material, pass through micro-wave digestion, intensified by ultrasonic wave point
Dissipate, microwave drying, microwave oxidizing roasting and microwave hydrogen reduction are prepared into Pd-Ni/ γ-Al2O3-SiO2Complex carrier bimetallic is urged
Agent, specifically includes following steps：
（S1）Micro-wave digestion：According to mass ratio it is 0.252 ~ 1.008 first by palladium bichloride and hydration nickel sulfate：0.680 ~ 6.80 adds
Enter into distilled water 2 ~ 5min of micro-wave digestion at normal temperatures to obtain clearing up mixed solution, wherein palladium bichloride quality and distilled water volume
Than for 0.252 ~ 1.008:200g/mL；
（S2）Intensified by ultrasonic wave disperses：To step（1）Clearing up for obtaining adds γ-Al in mixed solution2O3And SiO2It is well mixed
It is 10.0 ~ 12.0 to adjust pH, then in 40 under ultrasonic wave stirring action~60 DEG C of 10 ~ 60min of reaction, are filtered after the completion of reaction
Obtain filter cake, wherein γ-Al2O3And SiO2Mass ratio be 1 ~ 3:1；
（S3）S3.1 microwave dryings：By step（2）Obtained filter cake is warming up to 100 ~ 120 DEG C of microwave dryings in air atmosphere
30min；
S3.2 microwave oxidizing roastings：It is continuously heating to 450 ~ 650 DEG C of 30 ~ 120min of microwave oxidizing roasting；
S3.3 is passed through nitrogen and purges 10 ~ 20min, then passes to the mixed gas of hydrogen or hydrogen and nitrogen at 450 ~ 650 DEG C
React 30 ~ 60min, reaction naturally cools to temperature to close the mixed of hydrogen or hydrogen and nitrogen after less than 100 DEG C after terminating
Gas is closed, Pd-Ni/ γ-Al are obtained2O3-SiO2Complex carrier bimetallic catalyst.
The intake of hydrogen is 0.1 ~ 0.5L/min in above-mentioned S3.3.
The mixed gas intake of hydrogen and nitrogen is 0.4 ~ 6.0L/min, hydrogen and nitrogen mass ratio in above-mentioned S3.3
For 1:3.
The beneficial effects of the invention are as follows：
（1）The present invention utilizes Pd-Ni/ γ-Al2O3-SiO2The absorption hydrogen and catalytic hydrogenation reaction of complex carrier bimetallic catalyst
Characteristic, the combined chloride in catalytic dissociation bleaching shellac, which is prepared, can be used for the low-chlorine bleach lac of food and pharmaceutical industry.
（2）The characteristic that the present invention is heated using microwave selective and catalytic chemistry reacts, technical process is simple, dechlorination efficiency
It is high.
（3）The present invention is during low-chlorine bleach lac is prepared, the physicochemical property of the solvent and catalyst of addition to product
It is pollution-free, and material consumption and energy consumption are low, it is environment-friendly.
Embodiment
With reference to embodiment, the invention will be further described.
Embodiment 1
The method that the abjection combined chloride prepares low-chlorine bleach lac, it is comprised the following steps that：
（1）First by bleaching shellac（Chlorinty is 2.40wt%）It is 100 according to solid-to-liquid ratio:600g/mL is added to concentration
Bleaching shellac ethanol solution is obtained in 95wt% ethanol；
（2）To step（1）In obtained bleaching shellac ethanol solution according to solid-to-liquid ratio be 1.0:600g/mL addition Pd-Ni/ γ-
Al2O3-SiO2Bimetallic catalyst, then passes to hydrogen（Hydrogen flow rate is the hydrogen that 50mL/min, purity are 99.99%）,
Under the conditions of microwave irradiation after reaction terminates, bimetallic catalyst and filter are filtrated to get in reaction temperature to react at room temperature 120min
Liquid, filtrate is dried in vacuo after going out ethanol through vacuum distillation（It is that -0.08MPa, temperature are to dry 60min at 40 DEG C in pressure.）
To low-chlorine bleach lac, wherein Pd-Ni/ γ-Al2O3-SiO2Pd weight/mass percentage compositions are 0.5%, Ni matter in bimetallic catalyst
Amount percentage composition is 2.0%, γ-Al2O3With SiO2Mass ratio be 1:1.
Chlorinity is 0.46wt% in low-chlorine bleach lac after above-mentioned reaction.
Wherein Pd-Ni/ γ-Al2O3-SiO2The preparation method of bimetallic catalyst：
The carrier of bimetallic catalyst is A and B, and wherein A is γ type nano-aluminium oxides；Material B is that granularity is less than 0.841mm
Silica, to analyze pure palladium bichloride and analyze pure hydration nickel sulfate as raw material, pass through micro-wave digestion, intensified by ultrasonic wave point
Dissipate, microwave drying, microwave oxidizing roasting and microwave hydrogen reduction are prepared into Pd-Ni/ γ-Al2O3-SiO2Complex carrier bimetallic is urged
Agent, specifically includes following steps：
（S1）Micro-wave digestion：According to mass ratio it is 0.252 first by palladium bichloride and hydration nickel sulfate:2.720 it is added to distilled water
In at normal temperatures micro-wave digestion 2min obtain clearing up mixed solution, wherein palladium bichloride quality and distilled water volume ratio are 0.252:
200g/mL；
（S2）Intensified by ultrasonic wave disperses：To step（1）Clearing up for obtaining adds 15.0g γ-Al in mixed solution2O3With
15.0gSiO2Well mixed regulation pH is 10.0, then reacts 60min in 40 DEG C under ultrasonic wave stirring action, and reaction is completed
After be filtrated to get filter cake, wherein γ-Al2O3And SiO2Mass ratio be 1:1；
（S3）S3.1 microwave dryings：By step（2）Obtained filter cake is warming up to 100 DEG C of microwave drying 30min in air atmosphere；
S3.2 microwave oxidizing roastings：It is continuously heating to 450 DEG C of microwave oxidizing roasting 120min；
S3.3 is passed through nitrogen purging 10min, then passes to hydrogen and reacts 60min at 450 DEG C（The intake of hydrogen is 0.1L/
min）, reaction terminate after naturally cool to temperature be less than 100 DEG C after close hydrogen, obtain Pd-Ni/ γ-Al2O3-SiO2It is compound
Carrier bimetallic catalyst.
Embodiment 2
The method that the abjection combined chloride prepares low-chlorine bleach lac, it is comprised the following steps that：
（1）First by bleaching shellac（Chlorinty is 2.40wt%）It is 100 according to solid-to-liquid ratio:300g/ml is added to concentration
Bleaching shellac ethanol solution is obtained in 95wt% ethanol；
（2）To step（1）In obtained bleaching shellac ethanol solution according to solid-to-liquid ratio be 2.0:300g/ml addition Pd-Ni/ γ-
Al2O3-SiO2Bimetallic catalyst, then passes to hydrogen（Hydrogen flow rate is the hydrogen that 75mL/min, purity are 99.99%）,
It is 70 DEG C in reaction temperature under the conditions of microwave irradiation and reacts 30min, after reaction terminates, is filtrated to get bimetallic catalyst and filter
Liquid, filtrate is dried in vacuo after going out ethanol through vacuum distillation（It is that -0.08MPa, temperature are to dry 30min at 40 DEG C in pressure）Obtain
Low-chlorine bleach lac, wherein Pd-Ni/ γ-Al2O3-SiO2Pd weight/mass percentage compositions are 1%, Ni mass hundred in bimetallic catalyst
It is 2.0%, γ-Al to divide content2O3With SiO2Mass ratio be 2:1.
Chlorinity is 0.48wt% in low-chlorine bleach lac after above-mentioned reaction.
Wherein Pd-Ni/ γ-Al2O3-SiO2The preparation method of bimetallic catalyst：
The carrier of bimetallic catalyst is A and B, and wherein A is γ type nano-aluminium oxides；Material B is that granularity is less than 0.841mm
Silica, to analyze pure palladium bichloride and analyze pure hydration nickel sulfate as raw material, pass through micro-wave digestion, intensified by ultrasonic wave point
Dissipate, microwave drying, microwave oxidizing roasting and microwave hydrogen reduction are prepared into Pd-Ni/ γ-Al2O3-SiO2Complex carrier bimetallic is urged
Agent, specifically includes following steps：
（S1）Micro-wave digestion：According to mass ratio it is 0.504 first by palladium bichloride and hydration nickel sulfate:2.72 are added in distilled water
Micro-wave digestion 5min obtains clearing up mixed solution at normal temperatures, and wherein palladium bichloride quality and distilled water volume ratio are 0.504:
200g/mL；
（S2）Intensified by ultrasonic wave disperses：To step（1）Clearing up for obtaining adds 20.0g γ-Al in mixed solution2O3With
10.0gSiO2Well mixed regulation pH is 12.0, then reacts 10min in 60 DEG C under ultrasonic wave stirring action, and reaction is completed
After be filtrated to get filter cake, wherein γ-Al2O3And SiO2Mass ratio be 2:1；
（S3）S3.1 microwave dryings：By step（2）Obtained filter cake is warming up to 120 DEG C of microwave drying 30min in air atmosphere；
S3.2 microwave oxidizing roastings：It is continuously heating to 650 DEG C of microwave oxidizing roasting 30min；
S3.3 is passed through nitrogen purging 20min, then passes to hydrogen and reacts 30min at 650 DEG C（The intake of hydrogen is 0.5L/
min）, reaction terminate after naturally cool to temperature be less than 100 DEG C after close hydrogen, obtain Pd-Ni/ γ-Al2O3-SiO2It is compound
Carrier bimetallic catalyst.
Embodiment 3
The method that the abjection combined chloride prepares low-chlorine bleach lac, it is comprised the following steps that：
（1）First by bleaching shellac（Chlorinty is 2.40wt%）It is 100 according to solid-to-liquid ratio:500g/mL is added to concentration
Bleaching shellac ethanol solution is obtained in 95wt% ethanol；
（2）To step（1）In obtained bleaching shellac ethanol solution according to solid-to-liquid ratio be 3:500g/mL addition Pd-Ni/ γ-
Al2O3-SiO2Bimetallic catalyst, then passes to hydrogen（Hydrogen flow rate is the hydrogen that 90mL/min, purity are 99.99%）,
It is 50 DEG C in reaction temperature under the conditions of microwave irradiation and reacts 60min, after reaction terminates, is filtrated to get bimetallic catalyst and filter
Liquid, filtrate is dried in vacuo after going out ethanol through vacuum distillation（It is that -0.08MPa, temperature are to dry 30min at 40 DEG C in pressure.）
To low-chlorine bleach lac, wherein Pd-Ni/ γ-Al2O3-SiO2Pd weight/mass percentage compositions are 0.5%, Ni matter in bimetallic catalyst
Amount percentage composition is 1.0%, γ-Al2O3With SiO2Mass ratio be 2:1.
Chlorinity is 0.46wt% in low-chlorine bleach lac after above-mentioned reaction.
Wherein Pd-Ni/ γ-Al2O3-SiO2The preparation method of bimetallic catalyst：
The carrier of bimetallic catalyst is A and B, and wherein A is γ type nano-aluminium oxides；Material B is that granularity is less than 0.841mm
Silica, to analyze pure palladium bichloride and analyze pure hydration nickel sulfate as raw material, pass through micro-wave digestion, intensified by ultrasonic wave point
Dissipate, microwave drying, microwave oxidizing roasting and microwave hydrogen reduction are prepared into Pd-Ni/ γ-Al2O3-SiO2Complex carrier bimetallic is urged
Agent, specifically includes following steps：
（S1）Micro-wave digestion：According to mass ratio it is 0.252 first by palladium bichloride and hydration nickel sulfate:1.36 are added in distilled water
Micro-wave digestion 4min obtains clearing up mixed solution at normal temperatures, and wherein palladium bichloride quality and distilled water volume ratio are 0.252:
200g/mL；
（S2）Intensified by ultrasonic wave disperses：To step（1）Clearing up for obtaining adds 20.0g γ-Al in mixed solution2O3With
10.0gSiO2Well mixed regulation pH is 11.5, then reacts 50min in 50 DEG C under ultrasonic wave stirring action, and reaction is completed
After be filtrated to get filter cake, wherein γ-Al2O3And SiO2Mass ratio be 2:1；
（S3）S3.1 microwave dryings：By step（2）Obtained filter cake is warming up to 110 DEG C of microwave drying 30min in air atmosphere；
S3.2 microwave oxidizing roastings：It is continuously heating to 550 DEG C of microwave oxidizing roasting 100min；
S3.3 is passed through nitrogen purging 20min, then passes to hydrogen and reacts 40min at 550 DEG C（The intake of hydrogen is 0.2L/
min）, reaction terminate after naturally cool to temperature be less than 100 DEG C after close hydrogen, obtain Pd-Ni/ γ-Al2O3-SiO2It is compound
Carrier bimetallic catalyst.
Embodiment 4
The method that the abjection combined chloride prepares low-chlorine bleach lac, it is comprised the following steps that：
（1）First by bleaching shellac（Chlorinty is 2.40wt%）It is 100 according to solid-to-liquid ratio:600g/mL is added to concentration
Bleaching shellac ethanol solution is obtained in 95wt% ethanol；
（2）To step（1）In obtained bleaching shellac ethanol solution according to solid-to-liquid ratio be 5:600g/mL addition Pd-Ni/ γ-
Al2O3-SiO2Bimetallic catalyst, then passes to hydrogen（Hydrogen flow rate is the hydrogen that 100mL/min, purity are 99.99%）,
It is 50 DEG C in reaction temperature under the conditions of microwave irradiation and reacts 100min, after reaction terminates, is filtrated to get bimetallic catalyst and filter
Liquid, filtrate is dried in vacuo after going out ethanol through vacuum distillation（It is that -0.08MPa, temperature are to dry 50min at 40 DEG C in pressure.）
To low-chlorine bleach lac, wherein Pd-Ni/ γ-Al2O3-SiO2Pd weight/mass percentage compositions are 0.5%, Ni matter in bimetallic catalyst
Amount percentage composition is 0.5%, γ-Al2O3With SiO2Mass ratio be 3:1.
Chlorinity is 0.45wt% in low-chlorine bleach lac after above-mentioned reaction.
The above-mentioned Pd-Ni/ γ-Al2O3-SiO2The preparation method of complex carrier bimetallic catalyst, the bimetallic catalytic
The carrier of agent is A and B, and wherein A is γ type nano-aluminium oxides；Material B is the silica that granularity is less than 0.841mm, with
It is raw material to analyze pure palladium bichloride and analyze pure hydration nickel sulfate, by micro-wave digestion, and intensified by ultrasonic wave disperses, microwave drying, micro-
Ripple oxidizing roasting and microwave hydrogen reduction, are prepared into Pd-Ni/ γ-Al2O3-SiO2Complex carrier bimetallic catalyst, is specifically included
Following steps：
（S1）Micro-wave digestion：According to mass ratio it is 0.252 first by palladium bichloride and hydration nickel sulfate:0.680 is added to distilled water
In at normal temperatures micro-wave digestion 2min obtain clearing up mixed solution, wherein palladium bichloride quality and distilled water volume ratio are 0.252：
200g/mL；
（S2）Intensified by ultrasonic wave disperses：To step（1）Clearing up for obtaining adds 22.5g γ-Al in mixed solution2O3With
7.5gSiO2Well mixed regulation pH is 10.0（20g/L sodium hydroxide solution regulation pH is added dropwise）, then stirred in ultrasonic wave
10min is reacted in 40 DEG C under effect, filter cake, wherein γ-Al are filtrated to get after the completion of reaction2O3And SiO2Mass ratio be 3:1；
（S3）S3.1 microwave dryings：By step（2）Obtained filter cake is warming up to 100 DEG C of microwave drying 30min in air atmosphere；
S3.2 microwave oxidizing roastings：It is continuously heating to 450 DEG C of microwave oxidizing roasting 120min；
S3.3 is passed through nitrogen purging 15min, then passes to the mixed gas of hydrogen and nitrogen（Hydrogen is 1 with nitrogen mass ratio:3,
The intake of mixed gas is 0.8L/min）60min is reacted at 450 DEG C, reaction naturally cools to temperature after terminating be less than 100
The mixed gas of hydrogen and nitrogen is closed after DEG C, Pd-Ni/ γ-Al are obtained2O3-SiO2Complex carrier bimetallic catalyst.
Embodiment 5
The method that the abjection combined chloride prepares low-chlorine bleach lac, it is comprised the following steps that：
（1）First by bleaching shellac（Chlorinty is 2.40wt%）It is 100 according to solid-to-liquid ratio:500g/mL is added to concentration
Bleaching shellac ethanol solution is obtained in 95wt% ethanol；
（2）To step（1）In obtained bleaching shellac ethanol solution according to solid-to-liquid ratio be 5:500g/mL addition Pd-Ni/ γ-
Al2O3-SiO2Bimetallic catalyst, then passes to hydrogen（Hydrogen flow rate is the hydrogen that 80mL/min, purity are 99.99%）,
It is 70 DEG C in reaction temperature under the conditions of microwave irradiation and reacts 80min, after reaction terminates, is filtrated to get bimetallic catalyst and filter
Liquid, filtrate is dried in vacuo after going out ethanol through vacuum distillation（It is that -0.08MPa, temperature are to dry 40min at 40 DEG C in pressure.）
To low-chlorine bleach lac, wherein Pd-Ni/ γ-Al2O3-SiO2Pd weight/mass percentage compositions are 1.89%, Ni matter in bimetallic catalyst
Amount percentage composition is 4.69%, γ-Al2O3With SiO2Mass ratio be 2:1.
Chlorinity is 0.46wt% in low-chlorine bleach lac after above-mentioned reaction.
The above-mentioned Pd-Ni/ γ-Al2O3-SiO2The preparation method of complex carrier bimetallic catalyst, the bimetallic catalytic
The carrier of agent is A and B, and wherein A is γ type nano-aluminium oxides；Material B is the silica that granularity is less than 0.841mm, with
It is raw material to analyze pure palladium bichloride and analyze pure hydration nickel sulfate, by micro-wave digestion, and intensified by ultrasonic wave disperses, microwave drying, micro-
Ripple oxidizing roasting and microwave hydrogen reduction, are prepared into Pd-Ni/ γ-Al2O3-SiO2Complex carrier bimetallic catalyst, is specifically included
Following steps：
（1）Micro-wave digestion：According to mass ratio it is 1.008 first by palladium bichloride and hydration nickel sulfate:6.80 are added in distilled water
Micro-wave digestion 5min obtains clearing up mixed solution at normal temperatures, and wherein palladium bichloride quality and distilled water volume ratio are 1.008:
200g/mL；
（2）Intensified by ultrasonic wave disperses：To step（1）Clearing up for obtaining adds 20.0g γ-Al in mixed solution2O3With
10.0gSiO2Well mixed regulation pH is 11.5（20g/L sodium hydroxide solution regulation pH is added dropwise）, then stirred in ultrasonic wave
60min is reacted in 60 DEG C under effect, filter cake, wherein γ-Al are filtrated to get after the completion of reaction2O3And SiO2Mass ratio be 2:1；
（3）S3.1 microwave dryings：By step（2）Obtained filter cake is warming up to 105 DEG C of microwave drying 30min in air atmosphere；
S3.2 microwave oxidizing roastings：It is continuously heating to 500 DEG C of microwave oxidizing roasting 90min；
S3.3 is passed through nitrogen purging 20min, then passes to mixed gas（Hydrogen is 1 with nitrogen mass ratio:3, mixed gas it is logical
Enter amount for 6L/min）450 DEG C react 60min, reaction terminate after naturally cool to temperature be less than 100 DEG C after close gaseous mixture
Body, obtains Pd-Ni/ γ-Al2O3-SiO2Complex carrier bimetallic catalyst.
The embodiment to the present invention is explained in detail above, but the present invention is not limited to above-mentioned embodiment party
Formula, in the knowledge that those of ordinary skill in the art possess, can also make on the premise of present inventive concept is not departed from
Go out various change.
Claims (4)
1. a kind of method that abjection combined chloride prepares low-chlorine bleach lac, it is characterised in that comprise the following steps that：
（1）First by bleaching shellac according to solid-to-liquid ratio be 100：300 ~ 600g/mL is added to concentration to be floated in 95wt% ethanol
Trillium glue ethanol solution；
（2）To step（1）In obtained bleaching shellac ethanol solution according to solid-to-liquid ratio be 1.0 ~ 5.0:300 ~ 600g/mL is added
Pd-Ni/γ-Al2O3-SiO2Bimetallic catalyst, then passes to hydrogen, under the conditions of microwave irradiation in reaction temperature be room temperature
To 70 DEG C of 30 ~ 120min of reaction, after reaction terminates, bimetallic catalyst and filtrate are filtrated to get, filtrate goes out second through vacuum distillation
Vacuum drying obtains low-chlorine bleach lac, wherein Pd-Ni/ γ-Al after alcohol2O3-SiO2Pd mass percentage contains in bimetallic catalyst
It is 0.5% ~ 5.0%, γ-Al to measure as 0.5% ~ 2.0%, Ni weight/mass percentage compositions2O3With SiO2Mass ratio be 1 ~ 3:1.
2. the method that abjection combined chloride according to claim 1 prepares low-chlorine bleach lac, it is characterised in that：The step
（2）The hydrogen that middle hydrogen flow rate is 50 ~ 100mL/min, purity is 99.99%.
3. the method that abjection combined chloride according to claim 1 prepares low-chlorine bleach lac, it is characterised in that：The step
（2）It in pressure be that -0.08MPa, temperature are 30 ~ 60min of drying at 40 DEG C that middle vacuum drying condition, which is,.
4. the method that abjection combined chloride according to claim 1 prepares low-chlorine bleach lac, it is characterised in that：The step
（2）Middle Pd-Ni/ γ-Al2O3-SiO2The preparation method of bimetallic catalyst：
The carrier of bimetallic catalyst is A and B, and wherein A is γ type nano-aluminium oxides；Material B is that granularity is less than 0.841mm
Silica, to analyze pure palladium bichloride and analyze pure hydration nickel sulfate as raw material, pass through micro-wave digestion, intensified by ultrasonic wave point
Dissipate, microwave drying, microwave oxidizing roasting and microwave hydrogen reduction are prepared into Pd-Ni/ γ-Al2O3-SiO2Complex carrier bimetallic is urged
Agent, specifically includes following steps：
（S1）Micro-wave digestion：According to mass ratio it is 0.252 ~ 1.008 first by palladium bichloride and hydration nickel sulfate：0.680 ~ 6.80 adds
Enter into distilled water 2 ~ 5min of micro-wave digestion at normal temperatures to obtain clearing up mixed solution, wherein palladium bichloride quality and distilled water volume
Than for 0.252 ~ 1.008：200g/mL；
（S2）Intensified by ultrasonic wave disperses：To step（1）Clearing up for obtaining adds γ-Al in mixed solution2O3And SiO2It is well mixed
It is 10.0 ~ 12.0 to adjust pH, then in 40 under ultrasonic wave stirring action~60 DEG C of 10 ~ 60min of reaction, are filtered after the completion of reaction
Obtain filter cake, wherein γ-Al2O3And SiO2Mass ratio be 1 ~ 3:1；
（S3）S3.1 microwave dryings：By step（2）Obtained filter cake is warming up to 100 ~ 120 DEG C of microwave dryings in air atmosphere
30min；
S3.2 microwave oxidizing roastings：It is continuously heating to 450 ~ 650 DEG C of 30 ~ 120min of microwave oxidizing roasting；
S3.3 is passed through nitrogen and purges 10 ~ 20min, then passes to the mixed gas of hydrogen or hydrogen and nitrogen at 450 ~ 650 DEG C
React 30 ~ 60min, reaction naturally cools to temperature to close the mixed of hydrogen or hydrogen and nitrogen after less than 100 DEG C after terminating
Gas is closed, Pd-Ni/ γ-Al are obtained2O3-SiO2Complex carrier bimetallic catalyst.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157828A (en) * | 2007-11-12 | 2008-04-09 | 昆明理工大学 | Method for preparing low-chlorine bleach lac |
| CN102553597A (en) * | 2010-12-22 | 2012-07-11 | 太原理工大学 | Preparation method of supported Ni-B amorphous catalyst for selective hydrogenation |
| CN104549236A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof |
| CN104822625A (en) * | 2013-09-17 | 2015-08-05 | 塔塔钢铁有限公司 | Process for synthesizng reduced graphene oxide on substrate from seedlac |
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2017
- 2017-04-25 CN CN201710275715.1A patent/CN106967365A/en active Pending
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|---|---|---|---|---|
| CN101157828A (en) * | 2007-11-12 | 2008-04-09 | 昆明理工大学 | Method for preparing low-chlorine bleach lac |
| CN102553597A (en) * | 2010-12-22 | 2012-07-11 | 太原理工大学 | Preparation method of supported Ni-B amorphous catalyst for selective hydrogenation |
| CN104822625A (en) * | 2013-09-17 | 2015-08-05 | 塔塔钢铁有限公司 | Process for synthesizng reduced graphene oxide on substrate from seedlac |
| CN104549236A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Hydrogenation catalyst and application thereof |
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