CN109651169A - The method for preparing cyclohexylamine - Google Patents
The method for preparing cyclohexylamine Download PDFInfo
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- CN109651169A CN109651169A CN201710934624.4A CN201710934624A CN109651169A CN 109651169 A CN109651169 A CN 109651169A CN 201710934624 A CN201710934624 A CN 201710934624A CN 109651169 A CN109651169 A CN 109651169A
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- cyclohexylamine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
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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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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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
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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
- B01J27/19—Molybdenum
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Abstract
The present invention relates to the methods for preparing cyclohexylamine, mainly solve the problems, such as that the yield of aniline catalytic hydrogenation synthesizing cyclohexane 1 amine in the prior art and selectivity are low.Using the method for preparing cyclohexylamine, it is included in the presence of aniline hydrogenation catalyst, is reacted to obtain cyclohexylamine as raw material using hydrogen and aniline, wherein the aniline hydrogenation catalyst includes carrier and active component, the carrier is P Modification Al2O3, active component includes Co element and promoter elements；The promoter elements include the technical solution selected from least one of alkaline-earth metal and group vib metal metallic element, preferably solve the problems, such as this, can be used in the industrial production of cyclohexylamine.
Description
Technical field
The present invention relates to the methods for preparing cyclohexylamine.
Background technique
Cyclohexylamine also known as hexahydrophthalic anilide, aminocyclohexane are a kind of colourless transparent liquids, have strong fish to smell as of rotten fish amine taste, energy
It is miscible with water and common organic solvents.It is important Organic Chemicals and fine-chemical intermediate, is mainly used in rubber
In glue auxiliary agent, food additives, anti-corrosion, papermaking, plastic processing and textile industry.
Foreign countries' production is concentrated mainly on western developed country and area with application, and main manufacturer has U.S.'s air products
Company, Celanese Corp., the manufacturer of the scales such as BASF Aktiengesellschaft, Beyer Co., Ltd not etc..But in Europe, due to by
The limitation of hydrogen feed, cyclohexylamine are constantly in non-starving condition.The production capacity of domestic production cyclohexylamine is close to 100,000 tons/year, master
Want producer to have: in Qingdao Jin Tianchang, Hebei Ji, Weifang development, Shandong it is permanent big etc..2010, the consuming capacity of China's cyclohexylamine
At 70,000 tons/year, with the rapid development of food additives honey element and rubber industry, the consumption of cyclohexylamine is all with average annual 10%
Above speed increases.
The process route of the preparation of cyclohexylamine is relatively more, mainly there is aniline catalytic hydrogenation method, nitrocyclohexane reduction method, chlorine
Ammonolysis process is catalyzed for hexamethylene catalysis ammonolysis process, cyclohexanol gas phase ammoniation process and cyclohexanone.
1. nitrocyclohexane reduction method: this method generates hexamethylene using nitrocyclohexane and hydrogen as raw material, using reducing agent
Amine, since nitrocyclohexane raw material is difficult to obtain, this method is eliminated substantially.2. chlorocyclohexane be catalyzed ammonolysis process: this method with
Chlorocyclohexane and ammonia are raw material, carry out catalysis reaction to it.Its process route is longer, and the selectivity of cyclohexylamine is poor, and anti-
Product is answered to contain hydrogen chloride, the requirement to equipment is very high.3. cyclohexanol gas phase ammoniation process: it is in nickel/SiO 2 catalyst
Under effect, cyclohexanol and ammonia liquid-phase hydrogenatin generate cyclohexylamine and dicyclohexyl amine, and the yield of product cyclohexylamine and dicyclohexyl amine is 3:
1, the conversion ratio of cyclohexanol is 70% or so, and the country is there is not yet industrialization report.4. aniline catalytic hydrogenation method: raw by raw material of benzene
The method for producing cyclohexylamine mainly includes that benzene one-step method directly produces two processes of aniline and aniline catalytic hydrogenation.Aniline catalysis adds
Hydrogen method has two kinds of process routes of normal pressure and pressurization.Two kinds of techniques all have the advantages of technical maturity, raw material is easy to get, but device is general
Property is small, can only production list one cyclohexylamine, it is impossible to be used in produce other organic amines；And there are aniline conversion per pass for the technique
The defects of low and cyclohexylamine poor selectivity.
But from the point of view of the easy sexual clorminance and prospect in the source from raw material, cost advantage and technique, aniline catalytic hydrogenation is more
With can operating space, therefore this method has obtained the favor of domestic and international research institution.The Mink etc. of Hungarian research institute
In " Hydrogenation of aniline to cyclohexylamine amine on NaOH-promoted or
Lanthana supported Nickel " in describe a variety of methods for preparing Ni catalyst that have studied, discovery is catalyzed in aniline
In the gas phase reaction for adding hydrogen cyclohexylamine, traditional Ni catalyst is added in NaOH auxiliary agent, the cyclohexylamine started choosing can be made
Selecting property improves 5% or so；Patent DE1975457 (Hydrogenation process and hetaroganeous
catalysts for the preparation of mixtures of optionally sustituted
Cyclohexylamine and dicyclo-hexylamine fromthe correrponing anilines) it teaches
It is 100~350 DEG C, available very high by aniline plus the mixture of hydrogen cyclohexylamine and dicyclohexyl amine under conditions of 1~40MPa
Yield and selectivity.The carrier of the heterogeneous catalyst used in the reaction is Al2O3, active component is 0.50%~10%
Ru and Pd.Many research institutions all making an issue of on aniline catalytic hydrogenation catalyst in effort at present, but effect is unobvious, very
The difficult technical barrier and obstacle for successfully breaking aniline catalytic hydrogenation catalyst.I.e. above-mentioned existing method is in synthesizing cyclohexane 1 amine mistake
Cheng Zhongjun has that cyclohexylamine yield is low and selectivity is not high.
Summary of the invention
The technical problem to be solved by the present invention is to the low problems of the yield of cyclohexylamine and selectivity, provide a kind of new system
The method of standby cyclohexylamine, this method have the characteristics that cyclohexylamine high income and selectivity are high.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows:
The method for preparing cyclohexylamine is included in the presence of aniline hydrogenation catalyst, carries out using hydrogen and aniline as raw material anti-
Cyclohexylamine should be obtained, wherein the aniline hydrogenation catalyst includes carrier and active component, the carrier is P Modification Al2O3, living
Property component includes Co element and promoter elements；The promoter elements include in alkaline-earth metal and group vib metal
At least one metallic element.
In above-mentioned technical proposal, the molar ratio of hydrogen and aniline is preferably 20.0~40.0, and more preferably 25.0~35.0.
In above-mentioned technical proposal, the temperature of reaction is preferably 120~300 DEG C, and more preferable 185~220 DEG C.
In above-mentioned technical proposal, unstrpped gas volume space velocity is preferably 1800~3000h-1, more preferable 2100~2800h-1。
In above-mentioned technical proposal, the pressure of reaction is preferably 0.05~0.50MPa.
If not specializing, pressure of the present invention is in terms of gauge pressure.
In above-mentioned technical proposal, the Al of the modification2O3Phosphorus element content is preferably 0.10~3.00g/L in carrier, such as
But be not limited to 0.15,0.20,0.30,0.40,0.50,0.60,0.80,0.90,1.00,1.30,1.50,1.60,1.70,
1.80,1.90,2.00,2.50,2.90 etc., more preferable 0.80~2.00g/L.
In above-mentioned technical proposal, alkaline-earth metal preferably is selected from Be, Mg, Ca, Sr and Ba at least in the hydrogenation catalyst
One kind still more preferably includes Ca and Sr simultaneously.Ca and Sr has in terms of improving cyclohexylamine yield and cyclohexylamine selectivity
Synergistic effect.The ratio of Ca and Sr is not particularly limited, and the weight ratio of such as, but not limited to Ca and Sr are 0.10~10.00,
Within the scope of this non-limitative example of more specific weight ratio can be 0.20,0.40,0.50,0.60,0.80,1.00,1.20,
1.40、1.60、1.80、2.00、2.50、3.00、3.50、4.00、4.50、5.002、5.502、6.00、6.50、7.00、7.50、
8.00 etc..
In above-mentioned technical proposal, group vib metal preferably is selected from least one of Cr, Mo and W in the hydrogenation catalyst, more
It further preferably simultaneously include Cr and W.Cr and W has synergistic effect in terms of improving cyclohexylamine yield and cyclohexylamine selectivity.
The ratio of Cr and W is not particularly limited, and the weight ratio of such as, but not limited to Cr and W are 0.10~10.00, has more within this range
The non-limitative example of body weight ratio can be 0.20,0.40,0.50,0.60,0.80,1.00,1.20,1.40,1.60,
1.80,2.00,2.50,3.00,3.50,4.00,4.50,5.002,5.502,6.00,6.50,7.00,7.50,8.00 etc..
In above-mentioned technical proposal, the promoter elements preferably include at least one in alkali earth metal simultaneously
Kind and at least one of selected from group vib metallic element, metal member in the metallic element in alkaline-earth metal and group vib metal at this time
There is in terms of improving cyclohexylamine yield and cyclohexylamine selectivity synergistic effect between element.As non limiting example, such as but
Calcium is not limited to cooperate with chromium, calcium is cooperateed with tungsten etc..The ratio of alkali earth metal and group vib metallic element does not limit especially at this time
The weight ratio of system, such as, but not limited to alkali earth metal and group vib metallic element is 0.10~10.00, within this range more
The non-limitative example of specific weight ratio can be 0.20,0.40,0.50,0.60,0.80,1.00,1.20,1.40,1.60,
1.80,2.00,2.50,3.00,3.50,4.00,4.50,5.00,5.50,6.002,6.502,7.00,7.50,8.00 etc..
In above-mentioned technical proposal, the content of Co is preferably 1.00~8.00g/L in the hydrogenation catalyst, such as but unlimited
In, 1.50g/L, 2.00g/L, 2.50g/L, 3.00g/L, 3.50g/L, 4.00g/L, 4.50g/L, 5.00g/L, 5.50g/L,
6.00g/L, 6.50g/L, 7.00g/L, 7.50g/L etc., more preferably 1.50~5.00g/L.
In above-mentioned technical proposal, promoter elements content is preferably 0.50~10.00g/L in the hydrogenation catalyst,
Such as, but not limited to, 0.70g/L, 0.80g/L, 1.00g/L, 1.50g/L, 2.00g/L, 2.50g/L, 3.00g/L, 3.50g/L,
4.00g/L、4.50g/L、5.00g/L、5.50g/L、6.00g/L、6.50g/L、7.00g/L、7.50g/L、8.00g/L、
8.502g/L, 9.00g/L, 9.50g/L etc.；More preferably 1.00~6.00g/L.
In above-mentioned technical proposal, the carrier is preferably obtained using the method included the following steps:
(1) phosphorous compound is configured to aqueous solution dipping Al2O3, it is dried to obtain the precursor carrier I；
(2) above-mentioned precursor carrier I is roasted under reduction and/or inert atmosphere, obtains the modified support.
In above-mentioned technical proposal, the phosphorous compound preferably is selected from phosphoric acid, ammonium phosphate ((NH4)3PO4), diammonium hydrogen phosphate
((NH4)2HPO4And at least one of phosphorus pentoxide.Wherein the phosphoric acid preferably be selected from hypophosphorous acid, phosphorous acid, orthophosphoric acid,
At least one of at least one of pyrophosphoric acid, polyphosphoric acids, preferably orthophosphoric acid, pyrophosphoric acid, polyphosphoric acids.
In above-mentioned technical proposal, step (1) drying temperature is preferably 100~120 DEG C, such as, but not limited to 105 DEG C, 110
℃,115℃；Step (1) drying time preferably 3~10 hours, such as, but not limited to 4 hours, 5 hours, 6 hours, 7 hours, it is 8 small
When, 9 hours etc..
In above-mentioned technical proposal, the gas of step (2) is not specially required, and inert atmosphere can be 0 in the periodic table of elements
The inert gas (at least one of helium, neon and argon) and/or nitrogen, the reducibility gas of race can be hydrogen.
In above-mentioned technical proposal, step (2) maturing temperature is preferably 500~700 DEG C, such as, but not limited to 550 DEG C, 600
DEG C, 650 DEG C etc..The time of roasting preferably 3~10 hours, such as, but not limited to 4 hours, 5 hours, 6 hours, 7 hours, it is 8 small
When, 9 hours etc..
In above-mentioned technical proposal, the hydrogenation catalyst can be using the method preparation included the following steps:
(i) solution containing cobalt element and promoter elements is mixed by the composition of catalyst with carrier, obtains catalyst
Precursor；
(ii) it is dried to obtain the catalyst.
In above-mentioned technical proposal, as non-restrictive, the corresponding particular compound of step (i) cobalt element preferably is selected from vinegar
At least one of sour cobalt, ammonium cobaltous sulfate, cobalt chloride, cobalt nitrate, cobalt oxalate, cobaltous sulfate, cobalt carbonate and cobalt phosphate；More preferable sulphur
Sour cobalt ammonium.
In above-mentioned technical proposal, as non limiting example, the promoter elements in step (i) include alkaline-earth metal member
When plain, the corresponding particular compound of alkali earth metal preferably is selected from alkaline earth oxide, alkaline earth metal hydroxide, alkaline earth gold
Belong at least one of chloride, alkali earth metal sulfate, alkaline earth nitrate and Alkaline Earth Metal Acetate；More preferable alkaline earth
At least one of metal acetate salt；Most preferably from least one of calcium acetate and strontium acetate.
In above-mentioned technical proposal, as non limiting example, the promoter elements in step (i) include group vib metal
When element, the corresponding particular compound of group vib metallic element preferably is selected from chromic acetate, chromic nitrate, chromium chloride, ammonium molybdate, phosphoric
At least one of molybdenum, molybdenum carbonyl, molybdic acid, tungsten chloride, tungsten carbonyl, ammonium paratungstate and ammonium tungstate；More preferably from chromic acetate and tungsten
At least one of sour ammonium.
In above-mentioned technical proposal, step (ii) drying temperature is preferably 30~120 DEG C, such as, but not limited to 60 DEG C, 70 DEG C,
80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, more select 80~120 DEG C；Step (ii) drying time is preferably 1~5 hour, such as but not
It is limited to 1.5 hours, 2.0 hours, 2.5 hours, 3.0 hours, 3.5 hours, 4.0 hours, 4.5 hours etc..
Aniline can be obtained from commercially available channel, or the synthesis of phenylamino oxidizing process can be used.The side of synthesizing cyclohexane 1 amine of the present invention
In method, the suitable phenylamino oxidation catalyst of the known selection of those skilled in the art and determine suitable reaction temperature, when
Between and material proportion.For the such as, but not limited to active constituent of catalyst based on Ni or Cu, it is auxiliary ingredients that Ti, Cr etc., which is added,.
Carrier used can be active carbon, aluminium glue, silica gel or molecular sieve.
Preferred Ni-Ti/SiO in the present invention2For the catalyst of the direct ammoxidation reaction of benzene one-step method.Suitable Ni-Ti/
SiO2The content of nickel element preferably 2.50~5.00g/L in catalyst, more preferable 3.00~4.50g/L；The content of titanium elements is excellent
Select 0.50~3.00g/L, more preferable 1.00~2.00g/L.Suitable ammoxidation reaction temperature is preferably 80~350 DEG C；Ammonia
Oxidation pressure preferably 8.0~50.0MPa；The ammoxidation reaction time is preferably 0.5~5h；Benzene and hydroxylamine hydrochloride rub
That ratio preferably 0.5~3.0.After benzene ammoxidation, can the mixture to phenylamino oxidation carry out separation obtain mesh
Mark product aniline carries out catalytic hydrogenation again, can also be added with not separating directly to carry out being catalyzed after benzene ammoxidation generation aniline
Hydrogen.But cause system complexity convenient on year-on-year basis, the specific embodiment of the invention is all made of the progress of purified petroleum benzin amine to exclude other impurity
Catalytic hydrogenation.
The product mixtures of above-mentioned hydrogenation reaction can obtain target product cyclohexylamine through separation.
Product after hydrogenation reaction of the present invention is analyzed through gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), based on following equation
Calculate the yield and selectivity of cyclohexylamine:
Compared with prior art, the method for the present invention improves the yield and selectivity of cyclohexylamine.
The experimental results showed that cyclohexylamine yield selectively reaches 91.53% up to 81.58% when using the present invention, obtain
Preferable technical effect.Especially in catalyst carrier for hydrgenating P Modification, the active component of hydrogenation catalyst includes simultaneously
Cobalt selected from least one of alkaline-earth metal metallic element and when being selected from least one of group vib metal metallic element, obtains
Technical effect more outstanding.Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 2.32g4)2Co(SO4)2·6H2) and the calcium acetate (Ca of the Ca containing 1.75g O
(OAc)2·H2O aqueous solution 200ml) is immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Ca content 1.75g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 81.58%, and selectivity is 91.53%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
[embodiment 2]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 2.32g4)2Co(SO4)2·6H2) and the ammonium tungstate of the W containing 1.75g O
((NH4)10W12O41·4H2O it) is dissolved in hot water, obtains maceration extract 200ml and be immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, W content 1.75g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 81.41%, and selectivity is 91.70%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
[comparative example 1]
For the comparative example of [embodiment 1] and [embodiment 2].
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 2.32g4)2Co(SO4)2·6H2O) aqueous solution 200ml, 1L diameter 6mm, hole
Holding is 0.92cm3/ g, specific surface area 200cm2The Al of/g2O3On, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 70.05%, and selectivity is 83.17%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
By can be seen that the present invention compared with Examples 1 to 2 using phosphorous compound to support modification, and add hydrogen
Catalyst, active component is simultaneously using containing Co, Ca active component, catalyst performance containing Co, W active component is than only simultaneously
The performance of the active constituent catalyst containing Co is more excellent, illustrates activity of hydrocatalyst component while including using containing Co and selected from alkali
At least one of earth metal and group vib metal metallic element are conducive to the activity and stability that improve hydrogenation catalyst, hexamethylene
The yield and selectivity of amine will be high.
[comparative example 2]
For the comparative example of [comparative example 1].
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 2.32g4)2Co(SO4)2·6H2O) aqueous solution 200ml is immersed in P/
Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 72.77%, and selectivity is 85.26%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
The Al containing P Modification is used by can be seen that the present invention compared with comparative example 12O3Preparation plus hydrogen catalyst,
Than directly using Al2O3Preparation plus hydrogen catalyst, the performance of catalyst is more excellent, illustrates to use P/Al2O3Be conducive to aniline
Catalytic hydrogenation, the yield and selectivity of cyclohexylamine will be high.
[embodiment 3]
Modified support P/Al2O3Preparation:
(1) ammonium phosphate (NH of the P containing 0.80g4)3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei
0.92cm3/ g, specific surface area 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier
I。
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 0.80g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 2.32g4)2Co(SO4)2·6H2) and the beryllium acetate (Be of the Be containing 1.75g O
(OAc)2·H2O it) is dissolved in hot water, obtains maceration extract 200ml and be immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Be content 1.75g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 81.55%, and selectivity is 91.57%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
[embodiment 4]
Modified support P/Al2O3Preparation:
(1) the diammonium hydrogen phosphate ((NH of the P containing 2.00g4)2HPO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rong
For 0.92cm3/ g, specific surface area 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, before obtaining the carrier
Body I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 2.00g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 2.32g4)2Co(SO4)2·6H2) and the magnesium acetate (Mg of the Mg containing 1.75g O
(OAc)2·4H2O aqueous solution 200ml) is immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Mg content 1.75g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 81.56%, and selectivity is 91.50%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
[embodiment 5]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 2.32g4)2Co(SO4)2·6H2) and the barium acetate (Ba of the Ba containing 1.75g O
(OAc)2·H2O aqueous solution 200ml) is immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Ba content 1.75g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 81.52%, and selectivity is 91.55%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
[embodiment 6]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 2.32g4)2Co(SO4)2·6H2) and the strontium acetate (Sr of the Sr containing 1.75g O
(OAc)2·0.5H2O aqueous solution 200ml) is immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Sr content 1.75g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 81.61%, and selectivity is 91.51%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
[embodiment 7]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 2.32g4)2Co(SO4)2·6H2) and the chromic acetate (Cr of the Cr containing 1.75g O
(OAc)3·6H2O it) is dissolved in hot water, obtains maceration extract 200ml and be immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Cr content 1.75g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 81.45%, and selectivity is 91.66%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
[embodiment 8]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 1.50g4)2Co(SO4)2·6H2) and the ammonium molybdate of the Mo containing 1.00g O
((NH4)6Mo7O24·4H2O aqueous solution 200ml) is immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 1.50g/L, Mo content 1.00g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 185 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 79.97%, and selectivity is 90.84%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
[embodiment 9]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of the Co containing 5.00g4)2Co(SO4)2·6H2) and the ammonium paratungstate of the W containing 6.00g O
((NH4)10H2(W2O7)6·4H2O aqueous solution 200ml) is immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 3.00g/L, W content 6.00g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 220 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 81.11%, and selectivity is 90.14%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
[embodiment 10]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of Co containing 2.32g, W containing 1.12g and the Cr containing 0.63g4)2Co(SO4)2·6H2O)、
Ammonium tungstate ((NH4)10W12O41·4H2) and chromic acetate (Cr (OAc) O3·6H2O it) is dissolved in hot water, obtains maceration extract 200ml leaching
Stain is in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, W content 1.12g/L, Cr content 0.63g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 82.19%, and selectivity is 92.47%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 10 and embodiment 2 and embodiment 7, in yield and the selectivity side for improving cyclohexylamine
Face, in the hydrogenation catalyst that the present invention uses, metal elements W and metallic element Cr have preferable synergistic effect in group vib metal.
[embodiment 11]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of Co containing 2.32g, Ca containing 1.00g and the Sr containing 0.75g4)2Co(SO4)2·6H2O)、
Calcium acetate (Ca (OAc)2·H2) and strontium acetate (Sr (OAc) O2·0.5H2O aqueous solution 200ml) is immersed in P/Al2O3, obtain
Catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Ca content 1.00g/L, Sr content 0.75g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 82.51%, and selectivity is 92.08%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 11 and embodiment 1 and embodiment 6, in yield and the selectivity side for improving cyclohexylamine
Face, in the hydrogenation catalyst that the present invention uses, metallic element Ca and metallic element Sr have preferable synergistic effect in alkaline-earth metal.
[embodiment 12]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of Co containing 2.32g, Ca containing 0.91g and the W containing 0.84g4)2Co(SO4)2·6H2O)、
Calcium acetate (Ca (OAc)2·H2) and ammonium tungstate ((NH O4)10W12O41·4H2O it) is dissolved in hot water, obtains maceration extract 200ml dipping
In P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Ca content 0.91g/L, W content 0.84g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 83.01%, and selectivity is 92.77%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 12 and embodiment 1 and embodiment 2, in yield and the selectivity side for improving cyclohexylamine
Face, in the hydrogenation catalyst that the present invention uses, metallic element Ca has preferably in metal elements W and alkaline-earth metal in group vib metal
Synergistic effect.
[embodiment 13]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of Co containing 2.32g, Ca containing 0.91g and the Cr containing 0.84g4)2Co(SO4)2·6H2O)、
Calcium acetate (Ca (OAc)2·H2) and chromic acetate (Cr (OAc) O3·6H2O it) is dissolved in hot water, obtains maceration extract 200ml and be immersed in
P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Ca content 0.91g/L, Cr content 0.84g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 83.13%, and selectivity is 92.68%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 13 and embodiment 1 and embodiment 7, in yield and the selectivity side for improving cyclohexylamine
Face, in the hydrogenation catalyst that the present invention uses, metallic element Ca has preferably in metallic element Cr and alkaline-earth metal in group vib metal
Synergistic effect.
[embodiment 14]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of Co containing 2.32g, Ca containing 0.91g, W containing 0.50g and the Cr containing 0.34g4)2Co
(SO4)2·6H2O), calcium acetate (Ca (OAc)2·H2O), ammonium tungstate ((NH4)10W12O41·4H2) and chromic acetate (Cr (OAc) O3·
6H2O it) is dissolved in hot water, obtains maceration extract 200ml and be immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Ca content 0.91g/L, W content 0.50g/L, Cr content
0.34g/L。
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 84.37%, and selectivity is 93.59%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 14 and embodiment 12 and embodiment 13, in yield and the selectivity side for improving cyclohexylamine
Face, in the hydrogenation catalyst that the present invention uses, in group vib metal in metal elements W, Cr and alkaline-earth metal metallic element Ca have compared with
Good synergistic effect.
[embodiment 15]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate ((NH of Co containing 2.32g, Sr containing 0.91g, W containing 0.50g and the Cr containing 0.34g4)2Co
(SO4)2·6H2O), strontium acetate (Sr (OAc)2·0.5H2O), ammonium tungstate ((NH4)10W12O41·4H2) and chromic acetate (Cr O
(OAc)3·6H2O it) is dissolved in hot water, obtains maceration extract 200ml and be immersed in P/Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Sr content 0.91g/L, W content 0.50g/L, Cr content
0.34g/L。
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 84.42%, and selectivity is 93.49%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
[embodiment 16]
Modified support P/Al2O3Preparation:
(1) phosphoric acid (H of the P containing 1.52g3PO4) aqueous solution 180ml be immersed in 1L diameter 6mm, Kong Rongwei 0.92cm3/g、
Specific surface area is 200cm2The Al of/g2O3On, stand for 24 hours, 110 DEG C drying 4 hours, obtain the precursor carrier I.
(2) by precursor carrier I under nitrogen gas atmosphere 630 DEG C of roasting 5h, obtain the modified support P/Al2O3。
Measuring the P content in the carrier through ICP is 1.52g/L.
The preparation of hydrogenation catalyst:
(i) by the ammonium cobaltous sulfate of Co containing 2.32g, Ca containing 0.59g, Sr containing 0.32g, W containing 0.50g and the Cr containing 0.34g
((NH4)2Co(SO4)2·6H2O), calcium acetate (Ca (OAc)2·H2O), strontium acetate (Sr (OAc)2·0.5H2O), ammonium tungstate
((NH4)10W12O41·4H2) and chromic acetate (Cr (OAc) O3·6H2O it) is dissolved in hot water, obtains maceration extract 200ml and be immersed in P/
Al2O3, obtain catalyst precarsor I；
(ii) 110 DEG C drying 4 hours, obtain the catalyst.
The Co content for measuring the catalyst through ICP is 2.32g/L, Ca content 0.59g/L, Sr content 0.32g/L, W content
0.50g/L, Cr content 0.34g/L.
The synthesis of cyclohexylamine:
35ml catalyst is packed into microreactor, using nitrogen leak test, it is ensured that after system is without leak source, aniline is through measuring
Pump, which enters in vaporizer, to be vaporized, and controls 190 DEG C of vapourizing temperature of vaporizer, hydrogen along with aniline flow to vertical direction into
Enter vaporizer, unstripped gas is obtained after vaporizer mixes, hydrogen/aniline=30.0/1.0 (molar ratio) in unstripped gas.Then, former
Expect gas with 2400h-1Volume space velocity enter reactor, 188 DEG C of reaction temperature, reaction pressure (gauge pressure) 0.25MPa.After reaction
Mixed gas enters condenser from reactor bottom and is condensed, and analyzes product.
Yield through analytical calculation cyclohexylamine is 85.10%, and selectivity is 94.27%, for ease of description and is compared, will
Preparation, reaction condition, material inlet amount, cyclohexylamine yield and the selectivity of the support modification, hydrogenation catalyst of hydrogenation catalyst
It is listed in Tables 1 and 2 respectively.
Found out on year-on-year basis by embodiment 16 and embodiment 14 and embodiment 15, in yield and the selectivity side for improving cyclohexylamine
Face, in the hydrogenation catalyst that the present invention uses, metallic element Ca, Sr in metal elements W, Cr and alkaline-earth metal in group vib metal
There is preferable synergistic effect.
Table 1
Table 2
Claims (10)
1. the method for preparing cyclohexylamine is included in the presence of aniline hydrogenation catalyst, reacted using hydrogen and aniline as raw material
Cyclohexylamine is obtained, wherein the aniline hydrogenation catalyst includes carrier and active component, the carrier is P Modification Al2O3, activity
Component includes Co element and promoter elements；The promoter elements include in alkaline-earth metal and group vib metal
At least one metallic element.
2. the method according to claim 1 for preparing cyclohexylamine, it is characterized in that the molar ratio of hydrogen and aniline be 20.0~
40.0。
3. the method according to claim 1 for preparing cyclohexylamine, it is characterized in that the temperature of reaction is 120~300 DEG C.
4. the method according to claim 1 for preparing cyclohexylamine, it is characterized in that unstrpped gas volume space velocity is preferably 1800
~3000h-1。
5. the method according to claim 1 for preparing cyclohexylamine, it is characterized in that the pressure of reaction is 0.05~0.50MPa.
6. the method according to claim 1 for preparing cyclohexylamine, it is characterised in that phosphorus member in the catalyst carrier for hydrgenating
Cellulose content is 0.10~3.00g/L.
7. the method according to claim 1 for preparing cyclohexylamine, it is characterised in that alkaline-earth metal in the hydrogenation catalyst
Selected from least one of Be, Mg, Ca, Sr and Ba.
8. the method according to claim 1 for preparing cyclohexylamine, it is characterised in that group vib metal in the hydrogenation catalyst
Selected from least one of Cr, Mo and W.
9. the method according to claim 1 for preparing cyclohexylamine, it is characterised in that Co element contains in the hydrogenation catalyst
Amount is 1.00~8.00g/L.
10. the method according to claim 1 for preparing cyclohexylamine, it is characterised in that promoter elements in hydrogenation catalyst
Content is 0.50~10.00g/L.
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