CN104628527B - A kind of method preparing hydroquinone - Google Patents
A kind of method preparing hydroquinone Download PDFInfo
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- CN104628527B CN104628527B CN201310561012.7A CN201310561012A CN104628527B CN 104628527 B CN104628527 B CN 104628527B CN 201310561012 A CN201310561012 A CN 201310561012A CN 104628527 B CN104628527 B CN 104628527B
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- parachlorophenol
- potassium hydroxide
- catalyst
- hydroquinone
- basic fluxing
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 46
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229940090668 parachlorophenol Drugs 0.000 claims abstract description 40
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000007787 solid Substances 0.000 claims abstract description 14
- 239000000047 product Substances 0.000 claims abstract description 7
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 7
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- PQDSQOCJSMICOM-UHFFFAOYSA-N [Cl].OC1=CC=CC=C1 Chemical compound [Cl].OC1=CC=CC=C1 PQDSQOCJSMICOM-UHFFFAOYSA-N 0.000 claims 1
- 238000000605 extraction Methods 0.000 claims 1
- -1 make catalyst Chemical compound 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 229910001950 potassium oxide Inorganic materials 0.000 description 12
- 238000006073 displacement reaction Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- LJSAJMXWXGSVNA-UHFFFAOYSA-N a805044 Chemical compound OC1=CC=C(O)C=C1.OC1=CC=C(O)C=C1 LJSAJMXWXGSVNA-UHFFFAOYSA-N 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- RFXSFVVPCLGHAU-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1.OC1=CC=CC=C1 RFXSFVVPCLGHAU-UHFFFAOYSA-N 0.000 description 1
- 229940106691 bisphenol a Drugs 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- C07C37/02—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 halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of method preparing hydroquinone, particularly make catalyst, the method that parachlorophenol and potassium hydroxide solution Basic fluxing raction prepare hydroquinone with load-type solid.The present invention uses load-type solid to make catalyst, and parachlorophenol and potassium hydroxide solution carry out Basic fluxing raction at a certain temperature；Alkali solution liquid, through catalyst is recovered by filtration, is applied mechanically；After filtrate is acidified to pH=2～3 with hydrochloric acid, with methyl iso-butyl ketone (MIBK) extractive reaction product, the content < 0.05% of raw material, product in raffinate.
Description
Technical field
The present invention relates to a kind of method preparing hydroquinone, particularly make catalyst with load-type solid,
The method that parachlorophenol and potassium hydroxide solution Basic fluxing raction prepare hydroquinone.
Background technology
Hydroquinone (Hydroquinone) is mainly used as the developer of photograph, medicine material, monomer storing
The polymerization inhibitor of process interpolation, rubber antioxidant, azo dye, anthraquinone dye, stabilizer, antioxidant etc..
The production method of hydroquinone has more than ten to plant, and the most industrialized mainly have aniline oxidizing process, two different
Propyl benzene peroxidating method, bisphenol-A method, phenol-hydrogen peroxide hydroxylating method.
Aniline oxidizing process is hydroquinone production method the earliest.Production process generally includes two-step reaction, i.e.
Aniline is oxidized to 1,4-benzoquinone through manganese dioxide (or sodium dichromate) in sulfuric acid medium, then will with iron powder in water
1,4-benzoquinone is reduced into hydroquinone, concentrated, decolour, crystallize, be dried and to obtain hydroquinone finished product.With aniline
Meter, the total recovery of hydroquinone about 85%.This method has technical maturity, reaction is easily controlled, yield and product
Purity advantages of higher.But consumption of raw materials is high, produce in process of production substantial amounts of manganese sulfate, sulfur waste liquor of ammonium and
Iron cement, environmental pollution is serious；The dilute sulfuric acid contained in reaction feed liquid is to equipment corrosion, and cost of equipment is high；This
Outward, promoter manganese recovery utilization rate is low.Abroad the most eliminate this method.China opened from the 1950's
Begin to produce hydroquinone, its production method commonly used aniline oxidizing process.
For the deficiency overcoming aniline oxidizing process hydroquinone preparation technology to exist, the present invention is solid with self-control support type
Body alkali is catalyst, uses parachlorophenol and potassium hydroxide alkaline hydrolysis process route, and alkali solution liquid filters and separates catalysis
Agent recovery, filtrate is acidified, isolated hydroquinone after solvent extraction.
Summary of the invention
Present invention aim to address present in existing aniline oxidizing process hydroquinone preparation technology not enough:
(1) complex process, equipment investment is high；
(2) waste liquid in production process, waste residue amount are big,；
(3) catalyst recovery utilization rate is low, and production cost is high.
The present invention provides a kind of homemade cheap, and the solid alkali as a catalyst of Heat stability is good is prepared benzene
The method of diphenol.By the comparison with aniline oxidizing process production technology, have the advantage that
(1) technique is simple, and workable, equipment investment is few；
(2) " three wastes " amount is substantially reduced；
(3) catalyst stability is high, recovery is effective, and production cost is low.
The present invention adopts the following technical scheme that:
The present invention uses load-type solid to make catalyst, and parachlorophenol and potassium hydroxide solution are in uniform temperature
Under carry out Basic fluxing raction；Alkali solution liquid, through catalyst is recovered by filtration, is applied mechanically；Filtrate is acidified to hydrochloric acid
After pH=2～3, with methyl iso-butyl ketone (MIBK) extractive reaction product, the content < 0.05% of raw material, product in raffinate；
Gained oil reservoir measures parachlorophenol and hydroquinone content, calculates feed stock conversion, hydroquinone selectivity.
In technique scheme:
(1) in load type solid body base catalyst, carrier selects zirconium oxide, calcium oxide, titanium oxide, molecular sieve etc.,
Preferential oxidation zirconium；
(2) presoma select potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, preferably potassium hydroxide,
Sodium hydroxide, carrier loaded after under 823K calcine 4 hours, Hami spy constant H can reach 26；
(3) potassium hydroxide solution concentration 5～50wt%, preferably 25～45wt%, more preferably 30～40wt%；
(4) parachlorophenol and potassium hydroxide mol ratio are 1:1～20, preferably 1:3～10, more preferably 1:5～
8；
(5) solid base catalyst and parachlorophenol mass ratio are 1:1～30, preferably 1:5～20, more preferably
1:10～15；
(6) Basic fluxing raction temperature is 155～255 DEG C, preferably 185～235 DEG C, more preferably 195～215 DEG C；
(7) the Basic fluxing raction time is 4～20 hours, preferably 8～14 hours, more preferably 10～12 hours.
Following embodiment be intended to explanation add solid base catalyst carry out be catalyzed parachlorophenol alkaline hydrolysis prepare to benzene
Diphenol, has that catalysis activity is high, it is low to consume, and feed stock conversion is high, selectivity of product is high rather than to this
The further restriction of invention.
Detailed description of the invention
Embodiment 1
Parachlorophenol 106.6g, 40% concentration hydrogen potassium oxide 581.0g, KOH/ZrO is put in 1L autoclave2
Catalyst 10.7g, heats up after nitrogen displacement, controls reaction temperature 215 DEG C, react 12 hours, alkali solution liquid
Through catalyst is recovered by filtration, filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 430g.Parachlorophenol conversion ratio
98.5%, hydroquinone selectivity 87.1%.
Comparative example 1
Putting into parachlorophenol 106.6g, 40% concentration hydrogen potassium oxide 581.0g in 1L autoclave, nitrogen is replaced
Rear intensification, control reaction temperature 215 DEG C, react 12 hours, alkali solution liquid through catalyst is recovered by filtration, filtrate
It is acidified to pH=2～3 with 35% concentrated hydrochloric acid 440g.Parachlorophenol conversion ratio 8.2%, hydroquinone selectivity
57.4%。
Embodiment 2
Parachlorophenol 21.3g, 10% concentration hydrogen potassium oxide 493.9g, NaOH/ZrO is put in 1L autoclave2
Catalyst 3.0g, heats up after nitrogen displacement, controls reaction temperature 210 DEG C, react 12 hours, alkali solution liquid warp
Catalyst is recovered by filtration, and filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 93.0g.Parachlorophenol conversion ratio
78.2%, hydroquinone selectivity 89.4%.
Embodiment 3
Parachlorophenol 79.9g, 25% concentration hydrogen potassium oxide 522.9g, Na is put in 1L autoclave2CO3/ZrO2
Catalyst 9.7g, heats up after nitrogen displacement, controls reaction temperature 220 DEG C, react 8 hours, alkali solution liquid warp
Catalyst is recovered by filtration, and filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 245.3g.Parachlorophenol conversion ratio
82.4%, hydroquinone selectivity 90.1%.
Embodiment 4
Parachlorophenol 101.1g, 35% concentration hydrogen potassium oxide 683.9g, K is put in 1L autoclave2CO3/ZrO2
Catalyst 5.5g, heats up after nitrogen displacement, controls reaction temperature 215 DEG C, react 12 hours, alkali solution liquid warp
Catalyst is recovered by filtration, and filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 447.5g.Parachlorophenol conversion ratio
71.6%, hydroquinone selectivity 86.3%.
Embodiment 5
Parachlorophenol 111.9g, 45% concentration hydrogen potassium oxide 539.5g, K is put in 1L autoclave2CO3/CaO
Catalyst 5.0g, heats up after nitrogen displacement, controls reaction temperature 220 DEG C, react 10 hours, alkali solution liquid warp
Catalyst is recovered by filtration, and filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 454.1g.Parachlorophenol conversion ratio
79.4%, hydroquinone selectivity 82.1%.
Embodiment 6
Parachlorophenol 72.7g, 30% concentration hydrogen potassium oxide 581.0g, KOH/CaO is put in 1L autoclave
Catalyst 21.4g, heats up after nitrogen displacement, controls reaction temperature 215 DEG C, react 12 hours, alkali solution liquid
Through catalyst is recovered by filtration, filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 325.6g.Parachlorophenol converts
Rate 88.6%, hydroquinone selectivity 86.3%.
Embodiment 7
Parachlorophenol 85.2g, 32% concentration hydrogen potassium oxide 581.0g, K is put in 1L autoclave2CO3/CaO
Catalyst 8.5g, heats up after nitrogen displacement, controls reaction temperature 185 DEG C, react 12 hours, alkali solution liquid warp
Catalyst is recovered by filtration, and filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 348.2g.Parachlorophenol conversion ratio
60.2%, hydroquinone selectivity 89.1%.
Embodiment 8
Parachlorophenol 101.2g, 40% concentration hydrogen potassium oxide 551.0g, NaOH/ZrO is put in 1L autoclave2
Catalyst 15.2g, heats up after nitrogen displacement, controls reaction temperature 235 DEG C, react 10 hours, alkali solution liquid
Through catalyst is recovered by filtration, filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 412.2g.Parachlorophenol converts
Rate 99.2%, hydroquinone selectivity 63.4%.
Embodiment 9
Parachlorophenol 106.6g, 45% concentration hydrogen potassium oxide 516.0g, K is put in 1L autoclave2CO3/ZrO2
Catalyst 12.7g, heats up after nitrogen displacement, controls reaction temperature 215 DEG C, react 8 hours, alkali solution liquid warp
Catalyst is recovered by filtration, and filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 434.4g.Parachlorophenol conversion ratio
94.2%, hydroquinone selectivity 81.5%.
Embodiment 10
Parachlorophenol 63.5g, 20% concentration hydrogen potassium oxide 581.0g, Na is put in 1L autoclave2CO3/ZrO2
Catalyst 9.6g, heats up after nitrogen displacement, controls reaction temperature 215 DEG C, react 16 hours, alkali solution liquid warp
Catalyst is recovered by filtration, and filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 218.4g.Parachlorophenol conversion ratio
77.5%, hydroquinone selectivity 89.2%.
Embodiment 11
Parachlorophenol 106.6g, 40% concentration hydrogen potassium oxide 581.0g, KOH/ZrO is put in 1L autoclave2
Catalyst 10.7g, heats up after nitrogen displacement, controls reaction temperature 215 DEG C, react 12 hours, alkali solution liquid
Through catalyst is recovered by filtration, filtrate is acidified to pH=2～3 with 35% concentrated hydrochloric acid 430g.Parachlorophenol conversion ratio,
Hydroquinone selectivity, recovery after catalyst filtration, data are shown in Table 1.
Data applied mechanically by table 1 catalyst
| Apply mechanically number of times | Parachlorophenol conversion ratio (%) | Hydroquinone selectivity (%) |
| 1 | 99.1 | 87.8 |
| 2 | 98.9 | 86.7 |
| 3 | 97.5 | 86.1 |
| 4 | 96.1 | 85.4 |
Claims (4)
1. the method preparing hydroquinone, it is characterised in that make catalyst with load-type solid, will
Parachlorophenol and potassium hydroxide solution carry out Basic fluxing raction；Alkali solution liquid reclaims catalyst after filtering and applies mechanically；
After filtrate is acidified to pH=2～3 with hydrochloric acid, product hydroquinone is obtained by extraction with methyl iso-butyl ketone (MIBK)；
In load type solid body base catalyst, carrier selects zirconium oxide, calcium oxide, titanium oxide, molecular sieve, and presoma selects
With potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate；Calcine 4 hours under 823K after carrier loaded,
Hami spy constant H reaches 26；Potassium hydroxide solution concentration is 5～50wt%, and parachlorophenol rubs with potassium hydroxide
You are 1:1～30 than for 1:1～20, solid base catalyst and parachlorophenol mass ratio, and Basic fluxing raction temperature is
155～255 DEG C, the Basic fluxing raction time is 4～20 hours.
The method preparing hydroquinone the most according to claim 1, it is characterised in that potassium hydroxide is molten
Liquid concentration is 25～45wt%, and parachlorophenol and potassium hydroxide mol ratio are 1:3～10, solid base catalyst with
Parachlorophenol mass ratio is 1:5～20, and Basic fluxing raction temperature is 185～235 DEG C, the Basic fluxing raction time be 8～
14 hours.
The method preparing hydroquinone the most according to claim 2, it is characterised in that potassium hydroxide is molten
Liquid concentration 30～40wt%, parachlorophenol and potassium hydroxide mol ratio are 1:5～8, solid base catalyst with to chlorine
Phenol mass ratio is 1:10～15, and Basic fluxing raction temperature is 195～215 DEG C, and the Basic fluxing raction time is 10～12
Hour.
The method preparing hydroquinone the most according to claim 1, it is characterised in that raffinate Central Plains
Material, the content < 0.05wt% of product.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2041592A (en) * | 1934-10-11 | 1936-05-19 | Pennsylvania Coal Products Com | Process of hydrolyzing chlor phenols |
| CN102675232A (en) * | 2012-05-17 | 2012-09-19 | 山东京博控股股份有限公司 | Synthetic method of 4-(6-chlorine-quinoxaline-2-yloxy)-phenol |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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