CN108794293A - A kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene - Google Patents
A kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene Download PDFInfo
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- CN108794293A CN108794293A CN201810681966.4A CN201810681966A CN108794293A CN 108794293 A CN108794293 A CN 108794293A CN 201810681966 A CN201810681966 A CN 201810681966A CN 108794293 A CN108794293 A CN 108794293A
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- benzene
- catalyst
- hexamethylene
- fixed bed
- inorganic salts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The present invention discloses a kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene, including Ni/ γ-Al2O3The preparation of catalyst, catalytic hydrogenation, rectifying, the operations such as vacuum distillation, utilize Ni/ γ-Al2O3 catalyst provided by the invention, not only high catalytic efficiency, catalyst production cost is low, and whole Catalytic processes, it is environmentally protective, industrial exhaust waste is few, relative to traditional handicraft, technical solution disclosed by the invention is more green, it is economical, environmental protection, the technical solution effectively prevents the drawbacks of preparing hexamethylene using metal catalysed processes instantly, the recycling that such as there is catalyst is difficult, service life is short, selection performance is low and metal ion easily causes many problems such as pollution.
Description
Technical field
The present invention relates to catalytic hydrogenation synthesizing cyclohexane 1 alkane, specifically a kind of benzene fixed bed serialization hydrogenation synthesis hexamethylene
Method.
Background technology
Hexamethylene is a kind of important Organic Chemicals, is the primary raw material of synthetic nylon -6 and nylon -66, together
When, hexamethylene also can generate adipic acid by oxidation, become the raw material for preparing plasticizer and polyurethane etc., at present industrial production
Hexamethylene is traditional metal catalysed processes, and there are the recycling of catalyst difficulties, and service life is short, selects performance low and metal
Ion easily causes many problems such as pollution, such as industrializes the common Pt-C catalyst systems of catalytic hydrogenation, not only expensive, raw
Produce it is of high cost, and Pt-C catalyst in catalytic hydrogenation catalyst be easy poisoning, lose catalytic effect.
It is a series of to be reported in succession about the improved research of catalyst process based on the defect of Pt-C catalyst systems, as in
State's Patent No.：CN201410573583.7, open one kind " Isosorbide-5-Nitrae-dimethyl hexahydrophthalate hydrogenation catalyst ", the technology
The catalyst that scheme obtains substitutes traditional Pt-C catalyst systems, but more valuable metal is still used in the catalyst system and catalyzing
Ruthenium (Ru), industrial production cost can not still reduce.
Meanwhile existing hexamethylene production technology mostly uses benzene catalytic hydrogenation, it is existing based on rock-steady structure specific to phenyl ring
Have that Catalytic processes reaction efficiency is low, complex process, production cost is higher.
In view of the shortcomings of the prior art, being badly in need of a kind of high catalytic activity, low-cost catalyst and matching with the catalyst
The catalytic hydrogenation production technology of conjunction.
Invention content
(1) the technical issues of solving
In view of the deficiency of the prior art, the present invention provides a kind of benzene fixed bed serialization hydrogenation synthesis hexamethylene
Method, not only processing step is simple for catalytic hydrogen reduction benzene disclosed by the invention to hexamethylene, catalytic efficiency reaction effect is high,
Catalyst usage amount is low, effectively overcomes the easy poisoning and deactivation of conventional metals catalyst, expensive defect.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene, includes the following steps：
S1, the Ni/ γ-Al by 5-6kg2O3Catalyst is added in fixed bed reactors；
S2, it is heated to the benzene heating of 1000-1200kg to be mixed into hydrogen after vapor state, forms benzene-hydrogen gas mixture
Afterwards, it is passed into fixed bed reactors and carries out catalysis reaction, control catalytic reaction temperature is 200-300 DEG C, control catalysis reaction
Pressure is 3-5MPa；
S4, after reaction, after being cooled to 5-10 DEG C, filter residue and filtrate is obtained by filtration in reaction solution, and filter residue recycles, filter
Liquid is spare；
S5, DMF-DMSO mixed solvent systems are added into the filtrate in step S4 after extraction, isolated organic layer,
Organic layer obtains the crude product solution of hexamethylene-benzene, the crude product solution of hexamethylene-benzene is after being evaporated off benzene after rectifying
Obtain final products hexamethylene, vacuum degree when control vacuum distillation is 0.05-0.07MPa, and temperature when vacuum distillation is 80-
90℃；
Ni/ γ-the Al2O3The carrier of catalyst is γ-Al2O3, including tri- kinds of active constituents of Ni, Fe and Cu, wherein Ni
Content be 20wt%, the content of Cu is 1.5wt%, and the content of Fe is 1.1wt%, and surplus is γ-Al2O3；The Ni/ γ-
Al2O3Steps are as follows for the preparation method of catalyst：
(a) Ni inorganic salts, inorganic salts containing Fe, inorganic salts containing Cu will be contained according to composition by weight proportioning to be dissolved in deionized water
Obtain dipping solution；
(b) by γ-Al2O3It is impregnated into the maceration extract in step (a) and obtains catalyst intermediate；
(c) catalyst intermediate in step (b) is reduced by Ni/ γ-Al using reducing agent2O3Catalyst.
Preferably, the molar ratio of hydrogen and benzene is 15-20 in the benzene-hydrogen gas mixture:1.
Preferably, the molar ratio of hydrogen and benzene is 15 in the benzene-hydrogen gas mixture:1.
Preferably, the mass ratio of DMF and DMSO is 1 in the DMF-DMSO mixed solvent systems:1.
Preferably, the Ni inorganic salts are nickel chloride, Fe inorganic salts are iron chloride, Cu inorganic salts are copper chloride.
Preferably, the reducing agent in the step (c) is hydrogen.
Advantageous effect
The present invention provides a kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene, utilization is provided by the invention
Ni/γ-Al2O3Catalyst, not only high catalytic efficiency, catalyst production cost is low, and whole Catalytic processes, environmentally protective, work
The exhaust waste of industry production is few, and relative to traditional handicraft, technical solution disclosed by the invention is more green, economical, environmentally friendly.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
The every other embodiment obtained under the premise of creative work, shall fall within the protection scope of the present invention.
Embodiment 1:
A kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene, includes the following steps：
S1, the Ni/ γ-Al by 5kg2O3Catalyst is added in fixed bed reactors；
S2, it is heated to the benzene heating of 1000kg to be mixed into hydrogen after vapor state, forms benzene-hydrogen gas mixture, benzene-hydrogen
The molar ratio of hydrogen and benzene is 15 in oxygen mixture:1, benzene-hydrogen gas mixture is passed into fixed bed reactors and is urged
Change reaction, control catalytic reaction temperature is 200 DEG C, and control catalysis reaction pressure is 3MPa；
S4, after reaction, after being cooled to 5 DEG C, filter residue and filtrate is obtained by filtration in reaction solution, and filter residue recycles, filtrate
It is spare；
S5, DMF-DMSO mixed solvent systems isolated organic layer after extraction is added into the filtrate in step S4,
Organic layer obtains the crude product solution of hexamethylene-benzene after rectifying, the crude product solution of hexamethylene-benzene after benzene is evaporated off,
Final products hexamethylene is obtained, the total recovery of hexamethylene is 65%.In vacuum distillation process, vacuum degree when control is evaporated under reduced pressure
For 0.07MPa, temperature when vacuum distillation is 90 DEG C.
Ni/ γ-the Al2O3The carrier of catalyst is γ-Al2O3, including tri- kinds of active constituents of Ni, Fe and Cu, wherein Ni
Content be 20wt%, the content of Cu is 1.5wt%, and the content of Fe is 1.1wt%, and surplus is γ-Al2O3；
Ni/ γ-the Al2O3Steps are as follows for the preparation method of catalyst：
(a) matched according to composition by weight nickel chloride, iron chloride, copper chloride be dissolved in deionized water obtain impregnating it is molten
Liquid；
(b) by γ-Al2O3It is impregnated into the maceration extract in step (a) and obtains catalyst intermediate；
(c) catalyst intermediate in step (b) is reduced by Ni/ γ-Al using reducing agent2O3Catalyst.
Embodiment 2:
A kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene, includes the following steps：
S1, the Ni/ γ-Al by 6kg2O3Catalyst is added in fixed bed reactors；
S2, it is heated to the benzene heating of 1200kg to be mixed into hydrogen after vapor state, forms benzene-hydrogen gas mixture, benzene-hydrogen
The molar ratio of hydrogen and benzene is 20 in oxygen mixture:1, benzene-hydrogen gas mixture is passed into fixed bed reactors and is urged
Change reaction, control catalytic reaction temperature is 300 DEG C, and control catalysis reaction pressure is 5MPa；
S4, after reaction, after being cooled to 10 DEG C, filter residue and filtrate is obtained by filtration in reaction solution, and filter residue recycles, filtrate
It is spare；
S5, DMF-DMSO mixed solvent systems isolated organic layer after extraction is added into the filtrate in step S4,
Organic layer obtains the crude product solution of hexamethylene-benzene, the crude product solution of hexamethylene-benzene is after being evaporated off benzene after rectifying
Final products hexamethylene is obtained, the total recovery of hexamethylene is 68%.In vacuum distillation process, vacuum degree when control is evaporated under reduced pressure
For 0.05MPa, temperature when vacuum distillation is 80 DEG C, wherein the weight ratio of DMF and DMSO in DMF-DMSO mixed solvent systems
It is 1:1；
Ni/ γ-the Al2O3The carrier of catalyst is γ-Al2O3, including tri- kinds of active constituents of Ni, Fe and Cu, wherein Ni
Content be 20wt%, the content of Cu is 1.5wt%, and the content of Fe is 1.1wt%, and surplus is γ-Al2O3；The Ni/ γ-
Al2O3Steps are as follows for the preparation method of catalyst：
(a) matched according to composition by weight nickel chloride, iron chloride, copper chloride be dissolved in deionized water obtain impregnating it is molten
Liquid；
(b) by γ-Al2O3It is impregnated into the maceration extract in step (a) and obtains catalyst intermediate；
(c) catalyst intermediate in step (b) is reduced by Ni/ γ-Al using reducing agent2O3Catalyst.
Embodiment 3:
A kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene, includes the following steps：
S1, the Ni/ γ-Al by 5-6kg2O3Catalyst is added in fixed bed reactors；
S2, it is heated to the benzene heating of 1100kg to be mixed into hydrogen after vapor state, forms benzene-hydrogen gas mixture, be passed through
To catalysis reaction is carried out in fixed bed reactors, control catalytic reaction temperature is 250 DEG C, and control catalysis reaction pressure is 4MPa；
S4, after reaction, after being cooled to 10 DEG C, filter residue and filtrate is obtained by filtration in reaction solution, and filter residue recycles, filtrate
It is spare；
S5, DMF-DMSO mixed solvent systems isolated organic layer after extraction is added into the filtrate in step S4,
Organic layer obtains the crude product solution of hexamethylene-benzene, the crude product solution of hexamethylene-benzene is after being evaporated off benzene after rectifying
Final products hexamethylene is obtained, the total recovery of hexamethylene is 68%.In vacuum distillation process, vacuum degree when control is evaporated under reduced pressure
For 0.06MPa, temperature when vacuum distillation is 85 DEG C, wherein the weight ratio of DMF and DMSO in DMF-DMSO mixed solvent systems
It is 1:1；
Ni/ γ-the Al2O3The carrier of catalyst is γ-Al2O3, including tri- kinds of active constituents of Ni, Fe and Cu, wherein Ni
Content be 20wt%, the content of Cu is 1.5wt%, and the content of Fe is 1.1wt%, and surplus is γ-Al2O3；The Ni/ γ-
Al2O3Steps are as follows for the preparation method of catalyst：
(a) Ni inorganic salts, inorganic salts containing Fe, inorganic salts containing Cu will be contained according to composition by weight proportioning to be dissolved in deionized water
Obtain dipping solution；
(b) by γ-Al2O3It is impregnated into the maceration extract in step (a) and obtains catalyst intermediate；
(c) catalyst intermediate in step (b) is reduced by Ni/ γ-Al using reducing agent2O3Catalyst.
Embodiment 4:
A kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene, includes the following steps：
S1, the Ni/ γ-Al by 5.5kg2O3Catalyst is added in fixed bed reactors；
S2, it is heated to the benzene heating of 1150kg to be mixed into hydrogen after vapor state, forms benzene-hydrogen gas mixture, be passed through
To catalysis reaction is carried out in fixed bed reactors, control catalytic reaction temperature is 250 DEG C, and control catalysis reaction pressure is
4.5MPa；
S4, after reaction, after being cooled to 8 DEG C, filter residue and filtrate is obtained by filtration in reaction solution, and filter residue recycles, filtrate
It is spare；
S5, DMF-DMSO mixed solvent systems isolated organic layer after extraction is added into the filtrate in step S4,
Organic layer obtains the crude product solution of hexamethylene-benzene, the crude product solution of hexamethylene-benzene is after being evaporated off benzene after rectifying
Final products hexamethylene is obtained, the total recovery of hexamethylene is 65%.In vacuum distillation process, vacuum degree when control is evaporated under reduced pressure
For 0.07MPa, temperature when vacuum distillation be 88 DEG C wherein, the weight ratio of DMF and DMSO in DMF-DMSO mixed solvent systems
It is 1:1；
Ni/ γ-the Al2O3The carrier of catalyst is γ-Al2O3, including tri- kinds of active constituents of Ni, Fe and Cu, wherein Ni
Content be 20wt%, the content of Cu is 1.5wt%, and the content of Fe is 1.1wt%, and surplus is γ-Al2O3；The Ni/ γ-
Al2O3Steps are as follows for the preparation method of catalyst：
(a) Ni inorganic salts, inorganic salts containing Fe, inorganic salts containing Cu will be contained according to composition by weight proportioning to be dissolved in deionized water
Obtain dipping solution；
(b) by γ-Al2O3It is impregnated into the maceration extract in step (a) and obtains catalyst intermediate；
(c) catalyst intermediate in step (b) is reduced by Ni/ γ-Al using reducing agent2O3Catalyst.
Embodiment 5:
A kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene, includes the following steps：
S1, the Ni/ γ-Al by 5.8kg2O3Catalyst is added in fixed bed reactors；
S2, it is heated to the benzene heating of 1180kg to be mixed into hydrogen after vapor state, forms benzene-hydrogen gas mixture, be passed through
To catalysis reaction is carried out in fixed bed reactors, control catalytic reaction temperature is 250 DEG C, and control catalysis reaction pressure is
3.5MPa；
S4, after reaction, after being cooled to 6 DEG C, filter residue and filtrate is obtained by filtration in reaction solution, and filter residue recycles, filtrate
It is spare；
S5, DMF-DMSO mixed solvent systems isolated organic layer after extraction is added into the filtrate in step S4,
Organic layer obtains the crude product solution of hexamethylene-benzene, the crude product solution of hexamethylene-benzene is after being evaporated off benzene after rectifying
Final products hexamethylene is obtained, the total recovery of hexamethylene is 68%.In vacuum distillation process, vacuum degree when control is evaporated under reduced pressure
For 0.06MPa, temperature when vacuum distillation is 88 DEG C, wherein the weight ratio of DMF and DMSO in DMF-DMSO mixed solvent systems
It is 1:1；
Ni/ γ-the Al2O3The carrier of catalyst is γ-Al2O3, including tri- kinds of active constituents of Ni, Fe and Cu, wherein Ni
Content be 20wt%, the content of Cu is 1.5wt%, and the content of Fe is 1.1wt%, and surplus is γ-Al2O3；The Ni/ γ-
Al2O3Steps are as follows for the preparation method of catalyst：
(a) Ni inorganic salts, inorganic salts containing Fe, inorganic salts containing Cu will be contained according to composition by weight proportioning to be dissolved in deionized water
Obtain dipping solution；
(b) by γ-Al2O3It is impregnated into the maceration extract in step (a) and obtains catalyst intermediate；
(c) catalyst intermediate in step (b) is reduced by Ni/ γ-Al using reducing agent2O3Catalyst.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations, although with reference to the foregoing embodiments
Invention is explained in detail, it will be understood by those of ordinary skill in the art that:It still can be to aforementioned each implementation
Technical solution recorded in example is modified or equivalent replacement of some of the technical features；And these modification or
It replaces, the spirit and scope for various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution.
Claims (6)
1. a kind of method of benzene fixed bed serialization hydrogenation synthesis hexamethylene, which is characterized in that include the following steps：
S1, the Ni/ γ-Al by 5-6kg2O3Catalyst is added in fixed bed reactors；
S2, it is heated to the benzene heating of 1000-1200kg to be mixed into hydrogen after vapor state, forms benzene-hydrogen gas mixture, be passed through
To catalysis reaction is carried out in fixed bed reactors, control catalytic reaction temperature is 200-300 DEG C, and control catalysis reaction pressure is 3-
5MPa；
S4, after reaction, after being cooled to 5-10 DEG C, filter residue and filtrate is obtained by filtration in reaction solution, and filter residue recycles, and filtrate is standby
With；
S5, DMF-DMSO mixed solvent systems are added into the filtrate in step S4 after extraction, isolated organic layer is organic
Layer obtains the crude product solution of hexamethylene-benzene, the crude product solution of hexamethylene-benzene obtains after benzene is evaporated off after rectifying
Final products hexamethylene, vacuum degree when control vacuum distillation is 0.05-0.07MPa, and temperature when vacuum distillation is 80-90
℃；
Ni/ γ-the Al2O3The carrier of catalyst is γ-Al2O3, including tri- kinds of active constituents of Ni, Fe and Cu, wherein Ni's contains
Amount is 20wt%, and the content of Cu is 1.5wt%, and the content of Fe is 1.1wt%, and surplus is γ-Al2O3；Ni/ γ-the Al2O3
Steps are as follows for the preparation method of catalyst：
(a) Ni inorganic salts, inorganic salts containing Fe, inorganic salts containing Cu will be contained according to composition by weight proportioning to be dissolved in deionized water and obtain
Dipping solution；
(b) by γ-Al2O3It is impregnated into the maceration extract in step (a) and obtains catalyst intermediate；
(c) catalyst intermediate in step (b) is reduced by Ni/ γ-Al using reducing agent2O3Catalyst.
2. the method for benzene fixed bed serialization hydrogenation synthesis hexamethylene according to claim 1, which is characterized in that described
The molar ratio of hydrogen and benzene is 15-20 in benzene-hydrogen gas mixture:1.
3. the method for benzene fixed bed serialization hydrogenation synthesis hexamethylene according to claim 2, which is characterized in that described-
The molar ratio of hydrogen and benzene is 15 in hydrogen gas mixture:1.
4. the method for benzene fixed bed serialization hydrogenation synthesis hexamethylene according to claim 1, which is characterized in that described
The mass ratio of DMF and DMSO is 1 in DMF-DMSO mixed solvent systems:1.
5. the method for benzene fixed bed serialization hydrogenation synthesis hexamethylene according to claim 1, which is characterized in that the Ni
Inorganic salts are nickel chloride, Fe inorganic salts are iron chloride, Cu inorganic salts are copper chloride.
6. the method for benzene fixed bed serialization hydrogenation synthesis hexamethylene according to claim 1, which is characterized in that the step
Suddenly the reducing agent in (c) is hydrogen.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030114723A1 (en) * | 1999-08-10 | 2003-06-19 | Huntsman Petrochemical Corporation | Manufacture of cyclohexane from benzene and a hydrogen source containing impurities |
| CN101612596A (en) * | 2009-07-14 | 2009-12-30 | 厦门大学 | A kind of method of reducing of solid catalyst precursor body |
| CN102921410A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method of cyclohexane noble metal Ru catalyst by benzene hydrogenation |
| CN104513121A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Method for preparing cyclohexane through hydrogenation of benzene |
| CN105688915A (en) * | 2016-04-13 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Dual-function catalyst for hydrogenating benzene rings and reducing carbonyl, preparation of dual-function catalyst and application thereof |
-
2018
- 2018-06-27 CN CN201810681966.4A patent/CN108794293A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030114723A1 (en) * | 1999-08-10 | 2003-06-19 | Huntsman Petrochemical Corporation | Manufacture of cyclohexane from benzene and a hydrogen source containing impurities |
| CN101612596A (en) * | 2009-07-14 | 2009-12-30 | 厦门大学 | A kind of method of reducing of solid catalyst precursor body |
| CN102921410A (en) * | 2012-11-20 | 2013-02-13 | 中国海洋石油总公司 | Preparation method of cyclohexane noble metal Ru catalyst by benzene hydrogenation |
| CN104513121A (en) * | 2013-09-30 | 2015-04-15 | 中国石油化工股份有限公司 | Method for preparing cyclohexane through hydrogenation of benzene |
| CN105688915A (en) * | 2016-04-13 | 2016-06-22 | 凯凌化工(张家港)有限公司 | Dual-function catalyst for hydrogenating benzene rings and reducing carbonyl, preparation of dual-function catalyst and application thereof |
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