CN107262150A - A kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst - Google Patents
A kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst Download PDFInfo
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- CN107262150A CN107262150A CN201710418072.1A CN201710418072A CN107262150A CN 107262150 A CN107262150 A CN 107262150A CN 201710418072 A CN201710418072 A CN 201710418072A CN 107262150 A CN107262150 A CN 107262150A
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- phenylene diamine
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229940018564 m-phenylenediamine Drugs 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 239000011973 solid acid Substances 0.000 title claims abstract description 31
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 25
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000011964 heteropoly acid Substances 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 238000010992 reflux Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 238000012545 processing Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000002803 maceration Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000003610 charcoal Substances 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 8
- 238000007711 solidification Methods 0.000 claims description 8
- 230000008023 solidification Effects 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims description 5
- 239000003245 coal Substances 0.000 claims description 4
- 235000013399 edible fruits Nutrition 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 2
- 229910017604 nitric acid Inorganic materials 0.000 claims 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052799 carbon Inorganic materials 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 229960001755 resorcinol Drugs 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 229940018563 3-aminophenol Drugs 0.000 abstract description 2
- 238000004939 coking Methods 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 19
- 238000000034 method Methods 0.000 description 11
- 150000007522 mineralic acids Chemical class 0.000 description 8
- 239000003377 acid catalyst Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000006073 displacement reaction Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000007791 liquid phase Substances 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 238000007171 acid catalysis Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/618—Surface area more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/638—Pore volume more than 1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/045—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen
- C07C37/05—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of a group bound to the ring by nitrogen by substitution of a NH2 group
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to m-phenylene diamine (MPD) production technical field, more particularly to a kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst.The preparation method of the m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst, it is characterized in that：Using acid solution to activated carbon powder carry out be heated to reflux washing, be washed with deionized water afterwards it is constant to pH value, add pretreating agent be heated to reflux processing, the activated carbon powder after processing be washed with deionized water it is constant to pH value, be dried in vacuo it is standby；Heteropoly acid maceration extract is added into activated carbon powder, the hot setting after filtering, being dried under reduced pressure of the powdered carbon after terminating is impregnated, that is, obtains product.Step of the present invention is simple, and the catalyst activity component load capacity that preparation reaches is easily controllable, catalytic activity is high, stability good, service life is long；By the products application in the reaction of preparing resorcin by hydrolyzing m-phenylenediamine and m-aminophenol, preferable conversion ratio and yield can be obtained, the generation of the side reactions such as polymerization coking can be effectively controlled.
Description
（One）Technical field
The present invention relates to m-phenylene diamine (MPD) production technical field, supported solid acid catalysis is used in more particularly to a kind of m-phenylene diamine (MPD) hydrolysis
The preparation method of agent.
（Two）Background technology
Resorcinol is a kind of important fine Organic Chemicals, be widely used in agricultural, dyestuff, coating, medicine, plastics,
The fields such as rubber, electronic chemical product.At present, the main preparation methods of resorcinol have sulfonated alkali fusion method, m-Diisopropylbenzene oxidation
Method and m-phenylene diamine (MPD) Hydrolyze method.Compared to first two production method, m-phenylene diamine (MPD) Hydrolyze method has benefited from raw material sources facility, work
Skill flow is succinct, technology maturation and of reduced contamination and be widely studied uses, the good application prospect of presentation.
Traditional m-phenylene diamine (MPD) Hydrolyze method is generally used as arylamine hydrolysis using inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid
Acid catalyst, its drawback is that acid consumption is big, subsequent treatment process is miscellaneous, and reaction system corrosivity it is strong thus to equipment material
It is required that it is higher, increase equipment investment.Thus how to solve above-mentioned there is problem as m-phenylene diamine (MPD) Hydrolyze method future development
Direction.
With the pay attention to day by day of countries in the world in recent years to the strategy of sustainable development, green chemistry chemical technology to chemical industry and
Environmental project brings revolutionary variation, to realize environment-friendly green chemical industry, researchs and develops new catalyst and catalysis process
The important topic referred to as currently paid close attention to.And compared with traditional inorganic acids catalyst, solid acid catalyst have it is nontoxic, pair set
It is standby to corrode advantage that is small and being easily isolated and recycled, therefore be an important channel for realizing environmental friendly catalysis new technology.
As important a member in solid acid catalyst, carried heteropoly acid catalyst had both inherited heteropoly acid catalysis activity
The advantage that high, corrosivity is small, pollution is low, solves heteropoly acid as polar molecule and is difficult what is separated and recovered from reaction system again
Problem, while add the utilization rate and stability of active component, and catalyst acidity can be according to the adjustment of loaded by heteropoly acid amount
Accurate control reacts the acid requirement needed to match；And it is used as carrier material using having the inert activated carbon of excellent chemical
Material so that carried heteropoly acid can be used separately as catalyst, can also be used cooperatively with traditional inorganic acids, while being easy to catalysis
The regeneration treatment of agent, operation format is flexible.
（Three）The content of the invention
The present invention is in order to make up the deficiencies in the prior art there is provided a kind of catalytic activity is high, stability is good, between service life length
The preparation method of phenylenediamine hydrolysis load-type solid acid catalyst.
The present invention is achieved through the following technical solutions：
A kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst, comprises the following steps：
（1）Activated carbon powder is carried out using acid solution to be heated to reflux washing, the activated carbon powder after cleaning is washed with deionized water to pH
Value it is constant, add pretreating agent be heated to reflux processing, the activated carbon powder after processing be washed with deionized water it is constant to pH value, very
Empty drying for standby；
（2）Toward through step（1）Handle and heteropoly acid maceration extract is added in obtained activated carbon powder, stirring at low speed, after dipping terminates
Charcoal carrying heteropolyacid catalyst is transferred in tube furnace after filtering, being dried under reduced pressure, the hot setting under the conditions of protective atmosphere, is produced
To activated carbon supported type solid acid catalyst, closed preservation.
The present invention prepares load-type solid acid catalyst using activated carbon as carrier, can be by controlling active component miscellaneous
The need for the load capacity regulating catalyst acid strength of polyacid, the hydrolysis to match m-phenylene diamine (MPD)；And carrier active carbon itself
It with excellent chemical stability, can be used alone, can also be used cooperatively with common inorganic acid, reduce reaction system pair and set
Standby corrosion, while reducing inorganic acid consumption, simplifies aftertreatment technology difficulty；Improve traditional m-phenylene diamine (MPD) Hydrolyze method
The simple acid catalyst for using the inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid as arylamine hydrolysis, acid consumption is big, subsequent treatment
Technique is miscellaneous, reaction system corrosivity strong, require equipment material defect high, that equipment investment is big.
The present invention more excellent technical scheme be：
Step（1）In, activated carbon powder is that specific surface area is 800-2000m2One in/g fruit shell carbon, carbo lignius and ature of coal charcoal
Kind, preferably specific surface area is 1200-1800m2/ g fruit shell carbon；Acid solution is mass concentration 5-50% hydrochloric acid, sulfuric acid and phosphoric acid
One kind in solution, preferred mass concentration 20-40% hydrochloric acid or sulfuric acid solution；Pretreating agent is mass concentration 5-50% nitre
One kind in acid, hydrogen peroxide, potassium permanganate, potassium peroxydisulfate, ammonium persulfate and potassium hydroxide, preferred mass concentration 20-40% nitre
Acid, hydrogen peroxide or ammonium persulfate.
Step（1）In, the heating-up temperature of pretreating agent is 40-90 DEG C, and preferably 65-80 DEG C, return time is 1-24h, excellent
Select 5-10h.
Step（2）In, heteropoly acid maceration extract is in mass concentration 1-30% phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid
One kind, preferred mass concentration 10-25% phosphotungstic acid or phosphomolybdic acid；Dip time is 2-48h；It is preferred that 15-30h.
Step（2）Middle protective atmosphere is one kind in nitrogen, argon gas and helium, preferably argon gas or helium；Solidification temperature is
300-800 DEG C, preferably 400-600 DEG C；Hardening time is 1-12h, preferably 5-10h.
Step of the present invention is simple, and the catalyst activity component load capacity prepared is easily controllable, catalytic activity is high, stably
The good, service life of property is long；In the reaction that the catalyst is applied to preparing resorcin by hydrolyzing m-phenylenediamine and m-aminophenol,
Preferable conversion ratio and yield can be obtained, can effectively suppress the generation of the side reactions such as polymerization coking, reaction selectivity is improved, and
The separation and recovery that reaction terminates rear catalyst is easily operated.
（Four）Embodiment
Embodiment 1：A kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst, specifically includes following steps：
（1）The hydrochloric acid solution of mass concentration 20% is used to contrast surface area for 1200m2/ g shell powdered carbon carries out being heated to reflux washing
Wash, clean after powdered carbon be washed with deionized water it is constant to pH, add mass concentration 20% salpeter solution be heated to reflux processing,
Heating-up temperature is 65 DEG C, and return time is 10h, and, vacuum drying constant to pH is washed with deionized water in the activated carbon powder after processing
It is standby；
（2）The Salkowski's solution 100g of mass concentration 10% is prepared, is added through step（1）Obtained shell powdered carbon 20g is handled, it is low
Speed stirring dipping 15h, the charcoal carrying heteropolyacid catalyst after dipping terminates is transferred in tube furnace after filtering, being dried under reduced pressure,
Hot setting under the conditions of argon gas atmosphere, solidification temperature is 400 DEG C, and hardening time is 10h, that is, obtains activated carbon supported type solid acid
Catalyst, closed preservation.By phenetic analysis, the specific surface area of catalyst is about 1120m2/ g, total hole volume is about 1.13cm
3/g, average pore size is about 4.2nm;Phosphotungstic acid actual negative carrying capacity is about 47%.
Catalyst activity evaluation experimental：The 8.3g concentrated sulfuric acids are dissolved in 300g deionized waters, 18.25g m-phenylene diamine (MPD)s are weighed
It is completely dissolved in above-mentioned dilution heat of sulfuric acid, is transferred in 500mL autoclaves, adds that 3.27g is above-mentioned to be prepared into kettle
Carried phospho-tungstic acid catalyst, repeats air 6 times in displacement kettle using nitrogen, starts stirring to 200rpm, be heated to 220 DEG C of dimensions
Hold 7hr.Cool to room temperature pressure release, by the fast filtering under nitrogen protection of the hydrolyzate containing catalyst；Filtrate is through height
Effect liquid phase chromatogram is analyzed：M-phenylene diamine (MPD) conversion ratio 99.8%, resorcinol yield is about 96.9%, higher than using traditional inorganic acids
（Sulfuric acid, hydrochloric acid, phosphoric acid）Technique（Traditional inorganic acids hydrolysis process resorcinol yield is 85-93%）.
Embodiment 2：A kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst, specifically includes following step
Suddenly：
（1）The sulfuric acid solution of mass concentration 40% is used to contrast surface area for 1800m2/ g shell powdered carbon carries out being heated to reflux washing
Wash, clean after powdered carbon be washed with deionized water it is constant to pH, add mass concentration 30% hydrogen peroxide be heated to reflux processing, plus
Hot temperature be 80 DEG C, return time is 5h, the activated carbon powder after processing be washed with deionized water it is constant to pH, be dried in vacuo it is standby
With；
（2）The phosphorus molybdenum acid solution 90g of mass concentration 25% is prepared, is added through step（1）Handle obtained shell powdered carbon 35g, low speed
Stirring dipping 30h, the charcoal carrying heteropolyacid catalyst after dipping terminates is transferred in tube furnace after filtering, being dried under reduced pressure, in helium
Hot setting under gas atmospheric condition, solidification temperature is 600 DEG C, and hardening time is 5h, that is, obtains activated carbon supported type solid acid and urge
Agent, closed preservation.Catalyst is determined by characterizing, and specific surface area is about 1785m2/ g, total hole volume is about 1.31cm3/g,
Average pore size is about 3.7nm;Phosphomolybdic acid actual negative carrying capacity is about 58%.
Catalyst stability evaluation experimental：The 14.7g concentrated sulfuric acids are dissolved in 300g deionized waters, 16.2g isophthalic two is weighed
Amine is completely dissolved in above-mentioned dilution heat of sulfuric acid, is transferred in 500mL autoclaves, and the load that 3.3g is prepared is added into kettle
Type phosphomolybdic acid catalyst, repeats air 6 times in displacement kettle using nitrogen, starts stirring to 250rpm, be heated to 215 DEG C of maintenances
8hr.Reaction cools to room temperature pressure release after terminating, by the fast filtering under nitrogen protection of the hydrolyzate containing catalyst,
Filtrate uses efficient liquid phase chromatographic analysis, and the catalyst filtered is reused 5 times according to above-mentioned experiment condition.Through liquid chromatogram point
Analysis, 5 experiment m-phenylene diamine (MPD) conversion ratios and resorcinol yield are as shown in the table：
The data in table, catalyst is reused 5 times, and m-phenylene diamine (MPD) conversion ratio and resorcinol yield are without substantially drop
It is low；Catalyst after reusing 5 times is through analysis, and specific surface area is about 1702m2/ g, total hole volume is about 1.28cm3/g, is put down
Equal aperture is about 3.8nm;Phosphomolybdic acid actual negative carrying capacity is about 56.7%, and active component is lost in without obvious solution-off, and stability is good.
Embodiment 3：A kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst, specifically includes following step
Suddenly：
（1）30% hydrochloric acid solution is used to contrast surface area for 1500m2/ g shell powdered carbon carries out being heated to reflux washing, after cleaning
Powdered carbon be washed with deionized water it is constant to pH, add mass concentration 30% ammonium persulfate solution be heated to reflux processing, heating temperature
Spend for 72 DEG C, return time is 8h, the activated carbon powder after processing be washed with deionized water it is constant to pH, be dried in vacuo it is standby；
（2）The Salkowski's solution 200g of mass concentration 15% is prepared, is added through step（1）Obtained shell powdered carbon about 80g is handled,
Stirring at low speed impregnates 22h, and the charcoal carrying heteropolyacid catalyst after dipping terminates is transferred in tube furnace after filtering, being dried under reduced pressure,
The hot setting under the conditions of helium atmosphere, solidification temperature is 500 DEG C, and hardening time is 8h, that is, obtains activated carbon supported type solid
Acid catalyst, closed preservation.Catalyst is determined by characterizing, and specific surface area is about 1422m2/ g, total hole volume is about 1.09cm
3/g, average pore size is about 4.1nm；Phosphotungstic acid actual negative carrying capacity is about 32.5%.
Catalyst activity evaluation experimental：19.73g hydrochloric acid is dissolved in 250g deionized waters, 21.6g m-phenylene diamine (MPD)s are weighed complete
Be dissolved in above-mentioned dilute hydrochloric acid solution, be transferred in 500mL autoclaves entirely, added into kettle 4.37g it is above-mentioned prepare it is negative
Load type phosphotungstic acid catalyst, repeats air 6 times in displacement kettle using nitrogen, starts stirring to 300rpm, be heated to 220 DEG C of maintenances
6hr.Cool to room temperature pressure release, by the fast filtering under nitrogen protection of the hydrolyzate containing catalyst；Filtrate is through efficient
Liquid-phase chromatographic analysis：M-phenylene diamine (MPD) conversion ratio 99.6%, resorcinol yield is about 96.1%.
Embodiment 4：A kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst, specifically includes following step
Suddenly：
（1）The sulfuric acid solution of mass concentration 5% is used to contrast surface area for 800m2/ g wooden powdered carbon carries out being heated to reflux washing,
Clean after powdered carbon be washed with deionized water it is constant to pH, add mass concentration 5% potassium hydroxide solution be heated to reflux processing,
Heating-up temperature is 40 DEG C, and return time is 24h, and, vacuum drying constant to pH is washed with deionized water in the activated carbon powder after processing
It is standby；
（2）The silico-tungstic acid solution 80g of mass concentration 1% is prepared, is added through step（1）Handle obtained wooden powdered carbon 30g, low speed
Stirring dipping 48h, the charcoal carrying heteropolyacid catalyst after dipping terminates is transferred in tube furnace after filtering, being dried under reduced pressure, in nitrogen
Hot setting under gas atmospheric condition, solidification temperature is 300 DEG C, and hardening time is 12h, that is, obtains activated carbon supported type solid acid and urge
Agent, closed preservation.Catalyst is determined by characterizing, and specific surface area is about 775m2/ g, total hole volume is about 0.65cm3/g, is put down
Equal aperture is about 3.5nm；Silico-tungstic acid actual negative carrying capacity is about 22%.
Catalyst activity evaluation experimental：13.1g phosphoric acid is dissolved in 200g deionized waters, 12.96g m-phenylene diamine (MPD)s are weighed complete
It is dissolved in above-mentioned phosphoric acid solution, is transferred in 500mL autoclaves entirely, the above-mentioned loads prepared of 3.39g is added into kettle
Type silicotungstic acid catalyst, repeats air 6 times in displacement kettle using nitrogen, starts stirring to 300rpm, be heated to 220 DEG C of maintenances
6hr.Cool to room temperature pressure release, by the fast filtering under nitrogen protection of the hydrolyzate containing catalyst；Filtrate is through efficient
Liquid-phase chromatographic analysis：M-phenylene diamine (MPD) conversion ratio 99.2%, resorcinol yield is about 95.6%.
Embodiment 5：A kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst, specifically includes following step
Suddenly：
（1）The phosphoric acid solution of mass concentration 50% is used to contrast surface area for 2000m2/ g ature of coal powdered carbon carries out being heated to reflux washing
Wash, clean after powdered carbon be washed with deionized water it is constant to pH, add mass concentration 50% liquor potassic permanganate be heated to reflux place
Reason, heating-up temperature be 90 DEG C, return time is 1h, the activated carbon powder after processing be washed with deionized water it is constant to pH, vacuum do
It is dry standby；
（2）The silicomolybdic acid solution 50g of mass concentration 30% is prepared, is added through step（1）Handle obtained ature of coal powdered carbon 18g, low speed
Stirring dipping 2h, the charcoal carrying heteropolyacid catalyst after dipping terminates is transferred in tube furnace after filtering, being dried under reduced pressure, in nitrogen
Hot setting under atmospheric condition, solidification temperature is 800 DEG C, and hardening time is 1h, that is, obtains activated carbon supported type solid acid catalysis
Agent, closed preservation.Catalyst is determined by characterizing, and specific surface area is about 1825m2/ g, total hole volume is about 0.93cm3/g, is put down
Equal aperture is about 5.1nm；Silicomolybdic acid actual negative carrying capacity is about 70.4%.
Catalyst activity evaluation experimental：Weigh 27g m-phenylene diamine (MPD)s to be completely dissolved in 350g deionized waters, be transferred to 500mL
In autoclave, the above-mentioned loaded type silicon molybdic acid catalyst prepared of 5.66g is added into kettle, displacement kettle is repeated using nitrogen
Interior air 6 times, starts stirring to 300rpm, is heated to 225 DEG C of maintenance 9hr.Cool to room temperature pressure release, will contain catalysis
The hydrolyzate of agent fast filtering under nitrogen protection；Filtrate is through efficient liquid phase chromatographic analysis：M-phenylene diamine (MPD) conversion ratio 99.2%,
Benzenediol yield is about 95.4%.
Claims (9)
1. a kind of preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst, it is characterized in that, comprise the following steps：
（1）Activated carbon powder is carried out using acid solution to be heated to reflux washing, the activated carbon powder after cleaning is washed with deionized water to pH value not
Become, add pretreating agent be heated to reflux processing, the activated carbon powder after processing be washed with deionized water it is constant to pH value, vacuum do
It is dry standby；（2）Toward through step（1）Handle and heteropoly acid maceration extract is added in obtained activated carbon powder, stirring at low speed, after dipping terminates
Charcoal carrying heteropolyacid catalyst be transferred to after filtering, being dried under reduced pressure in tube furnace, the hot setting under the conditions of protective atmosphere, i.e.,
Obtain activated carbon supported type solid acid catalyst, closed preservation.
2. the preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst according to claim 1, its feature exists
In：Step（1）In, activated carbon powder is that specific surface area is 800-2000m2One kind in/g fruit shell carbon, carbo lignius and ature of coal charcoal；
Acid solution is one kind in mass concentration 5-50% hydrochloric acid, sulfuric acid and phosphoric acid solution；Pretreating agent is mass concentration 5-50%'s
One kind in nitric acid, hydrogen peroxide, potassium permanganate, potassium peroxydisulfate, ammonium persulfate and potassium hydroxide.
3. the preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst according to claim 1, its feature exists
In：Step（1）In, the heating-up temperature of pretreating agent is 40-90 DEG C, and return time is 1-24h.
4. the preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst according to claim 1, its feature exists
In：Step（2）In, heteropoly acid maceration extract is one in mass concentration 1-30% phosphotungstic acid, phosphomolybdic acid, silico-tungstic acid, silicomolybdic acid
Kind, dip time is 2-48h.
5. the preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst according to claim 1, its feature exists
In：Step（2）Middle protective atmosphere is one kind in nitrogen, argon gas and helium, and solidification temperature is 300-800 DEG C, and hardening time is
1-12h。
6. the preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst according to claim 2, its feature exists
In：Step（1）In, activated carbon powder is that specific surface area is 1200-1800m2/ g fruit shell carbon；Acid solution is mass concentration 20-40%
Hydrochloric acid or sulfuric acid solution；Pretreating agent is mass concentration 20-40% nitric acid, hydrogen peroxide or ammonium persulfate.
7. the preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst according to claim 3, its feature exists
In：Step（1）In, the heating-up temperature of pretreating agent is 65-80 DEG C, and return time is 5-10h.
8. the preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst according to claim 4, its feature exists
In：Step（2）In, heteropoly acid maceration extract is mass concentration 10-25% phosphotungstic acid or phosphomolybdic acid, and dip time is 15-30h.
9. the preparation method of m-phenylene diamine (MPD) hydrolysis load-type solid acid catalyst according to claim 5, its feature exists
In：Step（2）Middle protective atmosphere is argon gas or helium, and solidification temperature is 400-600 DEG C, and hardening time is 5-10h.
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| CN108997088A (en) * | 2018-09-06 | 2018-12-14 | 青岛科技大学 | A method of resorcinol is recycled from m-phenylene diamine (MPD) hydrolysis waste residue |
| CN109046246A (en) * | 2018-09-06 | 2018-12-21 | 青岛科技大学 | A kind of resource utilization method of m-phenylene diamine (MPD) hydrolysis waste residue |
| CN114085132A (en) * | 2021-12-02 | 2022-02-25 | 湖北特腾新材料技术有限公司 | Preparation method of 2, 6-dihydroxytoluene |
| CN114591146A (en) * | 2020-12-03 | 2022-06-07 | 中国科学院大连化学物理研究所 | Method for preparing hydroquinone from p-aminophenol |
| KR102562980B1 (en) | 2022-10-25 | 2023-08-03 | 티케이지휴켐스 주식회사 | The method for producing resorcinol from meta-phenylenediamine using non-corrosive catalyst |
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| CN109046246A (en) * | 2018-09-06 | 2018-12-21 | 青岛科技大学 | A kind of resource utilization method of m-phenylene diamine (MPD) hydrolysis waste residue |
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| KR102562980B1 (en) | 2022-10-25 | 2023-08-03 | 티케이지휴켐스 주식회사 | The method for producing resorcinol from meta-phenylenediamine using non-corrosive catalyst |
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