CN1180882C - Cr-base catalyst for synthesizing low-carbon amines directly from synthetic gas and ammonia gas and its application - Google Patents

Cr-base catalyst for synthesizing low-carbon amines directly from synthetic gas and ammonia gas and its application Download PDF

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Publication number
CN1180882C
CN1180882C CNB001233629A CN00123362A CN1180882C CN 1180882 C CN1180882 C CN 1180882C CN B001233629 A CNB001233629 A CN B001233629A CN 00123362 A CN00123362 A CN 00123362A CN 1180882 C CN1180882 C CN 1180882C
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catalyst
ammonia
synthesis gas
amine
gas
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CN1356164A (en
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毅 王
王毅
丁云杰
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Abstract

The present invention relates to a Cr-base catalyst for directly synthesizing low-carbon amine from synthetic gas and ammonia gas, which comprises active components and a vector. The catalyst is characterized in that Al2O3 is used as the vector, Cr is used as the main active component, and Zn, Mn and an oxide of a rare earth element are used as modifying agents. The components of the catalyst have the following weight content: 5 to 60% of Cr2O3 active component and 1 to 30% of modifying agent. The synthetic gas and the ammonia gas in the catalyst can generate low-carbon amine (monomethyl amine, dimethylamine, trimethylamine, ethylamine, propylamine, etc.) with high selectivity and mainly generate the monomethyl amine.

Description

A kind of chromium-based catalysts is in the application from synthesis gas and the direct synthesizing low-carbon amine of ammonia
Technical field
The present invention relates to low-carbon amines synthetic technology, provide a kind of chromium-based catalysts in the application from synthesis gas and the direct synthesizing low-carbon amine of ammonia (methylamine, dimethylamine, trimethylamine, ethamine and propylamine etc.) especially.
Background technology
The aminating reaction of synthesis gas and ammonia is the effective ways that improve synthesis gas and ammonia value, is one of effective way of carbon resource optimization comprehensive utilization.On chromium-based catalysts, its product is monomethyl amine, dimethylamine, trimethylamine, ethamine and propylamine etc., can be used for the production of dyestuff, organic synthesis intermediate, rubber plastizing agent, medicine and agrochemical respectively directly or indirectly, and purposes is very extensive.For synthesizing of low-carbon (LC) organic amine, generally adopt the method for homogeneous phase organic synthesis on the traditional industry.At the end of the sixties and the beginning of the seventies, once there were several pieces of United States Patent (USP)s to report and utilize synthesis gas and ammonia on heterogeneous catalyst, to synthesize the method for organic amine.The active component of catalyst system therefor can be Fe (US 2,518,754 and US 3,726,926 etc.), and (US 4 for Rh-Fe, 250,116), and Zr or Hf (US 3,636, and 153 and US 3,646,148), and Pd, Ag, Pt, Cu etc. (US 3,410,904 and US 3,444,203).Containing on the catalyst of Fe, producing the amine product of the complexity of 1-22 C number, a lot of products do not have commercial value, and are difficult to separate.On other catalyst, reactive activity is not high yet, and does not further report.At home, do not see the research report that this respect is arranged always.
Summary of the invention
The purpose of this invention is to provide a kind of chromium-based catalysts in the application from synthesis gas and the direct synthesizing low-carbon amine of ammonia, on this catalyst, synthesis gas and ammonia can generate low-carbon amines (monomethyl amine, dimethylamine, trimethylamine, ethamine and propylamine etc.) by highly selective, and mainly are monomethyl amines.
The invention provides a kind of chromium-based catalysts in the application from synthesis gas and the direct synthesizing low-carbon amine of ammonia, chromium-based catalysts is made up of active constituent and carrier, it is characterized in that with Al 2O 3Being carrier, is main active component with the Cr element, makes modifier with the oxide of Zn, Mn or rare earth element; Each composition weight content of catalyst is: Cr 2O 3Active component 5～60%, modifier 1～30%.
Preparation of catalysts method provided by the present invention is that the soln using dipping technique as the soluble compound of catalytic component is supported on the carrier, it is characterized in that the dipping process strictness carries out in the following order:
1) with ball-type Al 2O 3Be broken into the 20-40 order, and carry out drying and roasting.Dry and roasting can be carried out routinely;
2) will be as the solution impregnating carrier that contains the Cr element 1 of active component), drying and roasting make Cr 2O 3/ Al 2O 3Catalyst, dry and roasting can be carried out routinely;
3) will be as the solution impregnation 2 that contains elements such as Zn, Mn or rare earth of modifier) in prepared Cr 2O 3/ Al 2O 3Catalyst, the oxide that makes with elements such as Zn, Mn or rare earths after drying and the roasting is the Cr of modifier 2O 3/ Al 2O 3Catalyst.Dry and roasting can be carried out routinely;
4) contain the Cr of two kinds of oxide modifiers 2O 3/ Al 2O 3Preparation of catalysts is undertaken by step impregnation method, promptly earlier with the solution impregnation Cr that contains a kind of modifier element 2O 3/ Al 2O 3Sample carries out the dipping second time with the solution that contains another kind of modifier element after drying and the roasting again, makes after drying and the roasting again.Contain higher Cr 2O 3The Cr of component 2O 3/ Al 2O 3Catalyst is also pressed the step impregnation method preparation.Dry and roasting can be carried out routinely;
5) under certain atmosphere, above-mentioned gained catalyst is reduced.
The dipping solution that contains active component Cr in the said process, the available aqueous solution that contains the oxysalt of Cr component.The dipping solution that contains modifier element Zn, Mn or rare earth etc., the available aqueous solution that contains the oxysalt of elements such as Zn, Mn or rare earth.In the above-mentioned catalyst preparation process, drying was carried out under 50～150 ℃ 1～10 hour usually.Roasting process carried out under 300～800 ℃ 1～10 hour.
A kind of chromium-based catalysts of the present invention is in the application from synthesis gas and the direct synthesizing low-carbon amine of ammonia, and reacting gas is the gaseous mixture of synthesis gas and ammonia, wherein CO in the synthesis gas: H 2=1: 0.5～1: 5 (volume ratio), and CO: NH 3=1: 0.1～1: 10 (volume ratio).The ratio that the gaseous mixture of synthesis gas and ammonia accounts for overall reaction gas is 5%～100% (volume fraction), and balanced gas is H 2Or N 2Reaction condition is: reaction temperature: 200～600 ℃, and reaction pressure: normal pressure～10Mpa, the ammonia air speed is 10～10000h -1Catalyst was used H before reaction 2Or H 2Gaseous mixture (H with Ar 2/ Ar=5: 95～50: 50, volume ratio) reduce.Common reducing condition is: 200～600 ℃ of reduction temperatures, the recovery time is 0.5～8 hour.
The specific embodiment
Below by example technology of the present invention is described further.
Example 1
Catalyst " A " consists of 40%Cr 2O 3Be supported on Al 2O 3On.The preparation method is as follows:
(1) Al 2O 3Processing
With ball-type Al 2O 3Carry out crushing and screening, get 20～40 purpose particles, earlier 120 ℃ of dryings 2 hours, 500 ℃ of roastings 5 hours under the air atmosphere in Muffle furnace then.
(2) 20%Cr 2O 3/ Al 2O 3Preparation of catalysts
Take by weighing 40.40 gram (NH 4) 2CrO 4, be dissolved in water and heat, about regulator solution volume to 100 milliliter, be immersed in the Al after the 112.5 gram roastings at normal temperatures 2O 3On the particle, in kept at room temperature overnight.120 ℃ of oven dry 4 hours, 450 ℃ of roastings 4 hours promptly got 20%Cr then 2O 3/ Al 2O 3Catalyst.
(3) 40%Cr 2O 3/ Al 2O 3Preparation of catalysts
Take by weighing 40.40 gram (NH 4) 2CrO 4, be dissolved in water and heat, about regulator solution volume to 100 milliliter, be immersed in the 20%Cr that makes in (2) at normal temperatures 2O 3/ Al 2O 3On the catalyst, in kept at room temperature overnight.120 ℃ of oven dry 4 hours, 450 ℃ of roastings 4 hours promptly got 40%Cr then 2O 3/ Al 2O 3Catalyst.The reactivity worth such as the table 1 of catalyst A
The synthesis gas aminating reaction performance of table 1 catalyst A
Reaction temperature CO changes amine and always selects amine always to receive product distribution (mol%)
Degree (℃) selecting property of change rate rate one first diformazan front three hydro carbons
(%) (%) (g/Kgcat. amine amine amine
h)
250 13.49 83.54 14.93 83.90 4.49 1.57 10.03
300 20.08 83.76 21.82 79.28 5.32 2.51 12.22
350 41.27 77.89 39.70 66.57 7.19 5.26 17.21
400 39.20 46.93 23.64 47.64 3.63 1.41 43.58
Reaction condition: reaction pressure: 0.6Mpa, ammonia dividing potential drop: 0.0316Mpa, air speed: 2000h -1
Embodiment 2
The main active component of catalyst " B " is identical with catalyst " A ", but has added ZnO as modifier, and its preparation process is as follows:
(1) 40%Cr 2O 3/ Al 2O 3Preparation of catalysts
Its process is identical with the preparation process of catalyst " A ".
(2) 40%Cr 2O 3-20%ZnO/Al 2O 3Preparation of catalysts
Take by weighing 82.24 gram Zn (NO 3) 26H 2O is dissolved in water and heats, and about regulator solution volume to 100 milliliter, is immersed in the 40%Cr that makes in (1) at normal temperatures 2O 3/ Al 2O 3On the catalyst, in kept at room temperature overnight.120 ℃ of oven dry 4 hours, 450 ℃ of roastings 4 hours promptly got 40%Cr then 2O 3-20%ZnO/Al 2O 3Catalyst.The aminating reaction performance such as the table 2 of catalyst " B ":
The synthesis gas aminating reaction performance of table 2 catalyst B
Reaction temperature CO changes amine and always selects amine always to receive product distribution (mol%)
Degree (℃) selecting property of change rate rate one first diformazan front three hydro carbons
(%) (%) (g/Kgcat. amine amine amine
h)
250 4.66 62.50 3.94 75.84 1.02 1.26 21.90
300 11.90 66.94 10.37 68.90 4.32 1.90 22.90
350 29.55 77.21 28.48 65.84 14.00 1.38 16.95
400 39.63 67.38 33.83 62.60 9.62 1.56 22.69
Reaction condition: reaction pressure: 0.6Mpa, ammonia dividing potential drop: 0.0316Mpa, air speed: 2000h -1
Embodiment 3
The main active component of catalyst " C " is identical with catalyst " A ", but has added MnO as modifier, and its preparation process is identical with " B ", just 82.24 gram Zn (NO 3) 26H 2O has changed the Mn (NO of 113.51 grams 50% into 3) 2Solution.The aminating reaction performance such as the table 3 of catalyst " C ": embodiment 2～3 explanation adds the total recovery that ZnO or MnO component can not improve conversion ratio and the amine of CO, can make activity of such catalysts that to a certain degree decline is arranged on the contrary.But make Cr after adding these two kinds of components 2O 3/ Al 2O 3The content of amine selectivity, yield and dimethylamine during the pyroreaction of catalyst increases, and the effect when especially adding ZnO is apparent in view.
The synthesis gas aminating reaction performance of table 3 catalyst C
Reaction temperature CO changes amine and always selects amine always to receive product distribution (mol%)
Degree (℃) selecting property of change rate rate one first diformazan front three hydro carbons
(%) (%) (g/Kgcat. amine amine amine
h)
250 2.78 62.39 2.36 75.72 2.55 0 21.74
300 8.46 64.89 7.20 70.57 3.16 2.43 17.41
350 25.14 69.41 21.98 63.85 10.23 1.63 36.10
400 40.45 46.98 23.96 45.72 9.40 0 37.56
Reaction condition: reaction pressure: 0.6Mpa, ammonia dividing potential drop: 0.0316Mpa, air speed: 2000h -1
Embodiment 4
The main active component of catalyst " D " is identical with catalyst " A ", but has added ZnO and CeO 2As modifier, its preparation process is as follows:
(1) 40%Cr 2O 3-20%ZnO/Al 2O 3Preparation of catalysts
Its process is identical with the preparation process of catalyst " B ".
(2) 40%Cr 2O 3-20%ZnO-2%CeO 2/ Al 2O 3Preparation of catalysts
Take by weighing 5.67 gram Ce (NO 3) 36H 2O is dissolved in water, and about regulator solution volume to 100 milliliter, is immersed in the 40%Cr that makes in (1) at normal temperatures 2O 3-20%ZnO/Al 2O 3On the catalyst, in kept at room temperature overnight.120 ℃ of oven dry 4 hours, 450 ℃ of roastings 4 hours promptly got 40%Cr then 2O 3-20%ZnO-2%CeO 2/ Al 2O 3Catalyst.The aminating reaction performance such as the table 4 of catalyst " D ":
The synthesis gas aminating reaction performance of table 4 catalyst D
Reaction temperature CO changes amine and always selects amine always to receive product distribution (mol%)
Degree (℃) selecting property of change rate rate one first diformazan front three hydro carbons
(%) (%) (g/Kgcat. amine amine amine
h)
250 3.52 56.97 2.61 66.32 3.51 2.57 27.60
300 14.81 50.90 9.50 51.40 4.06 2.38 39.00
350 32.50 57.38 23.15 49.90 10.86 1.07 35.59
Reaction condition: reaction pressure: 0.6Mpa, ammonia dividing potential drop: 0.0316Mpa, air speed: 2000h -1
Embodiment 5
The main active component of catalyst " E " is identical with catalyst " A ", but has added ZnO and MnO as modifier, and its preparation process is identical with " D ", just 5.67 gram Ce (NO 3) 36H 2O has changed the 50%Mn (NO of 11.35 grams into 3) 2Solution.The aminating reaction performance such as the table 5 of catalyst " E ":
The synthesis gas aminating reaction performance of table 5 catalyst E
Reaction temperature CO changes amine and always selects amine always to receive product distribution (mol%)
Degree (℃) selecting property of change rate rate one first diformazan front three hydro carbons
(%) (%) (g/Kgcat. amine amine amine
h)
250 5.10 41.52 2.81 53.64 1.72 1.34 43.26
300 17.20 46.72 9.93 45.91 3.93 2.57 43.45
350 37.58 50.56 23.09 40.17 13.85 0 43.04
Reaction condition: reaction pressure: 0.6Mpa, ammonia dividing potential drop: 0.0316Mpa, air speed: 2000h -1
Embodiment 4～5 shows at ZnO-Cr 2O 3/ Al 2O 3Further add CeO on the catalyst 2Or MnO makes the conversion ratio of CO that raising is arranged slightly, and effect is apparent in view when especially adding MnO.
But both addings all make the overall selectivity of amine and yield thereof descend to some extent, and hydrocarbon production improves.

Claims (5)

1, a kind of chromium-based catalysts is in the application from synthesis gas and the direct synthesizing low-carbon amine of ammonia, and chromium-based catalysts is made up of active constituent and carrier, it is characterized in that with Al 2O 3Being carrier, is main active component with the Cr element, makes modifier with the oxide of Zn, Mn or rare earth element; Each composition weight content of catalyst is: Cr 2O 3Active component 5～60%, modifier 1～30%.
2, according to the described chromium-based catalysts of claim 1 in the application from synthesis gas and the direct synthesizing low-carbon amine of ammonia, it is characterized in that the preparation process of described chromium-based catalysts is as follows:
(1) with carrier A l 2O 3Be broken into the 20-40 order, and carry out drying and roasting;
(2) as the solution impregnating carrier that contains the Cr element (1) of active component, drying and roasting make Cr 2O 3/ Al 2O 3Catalyst;
(3) as prepared Cr in the solution impregnation that contains Zn, Mn or rare earth element (2) of modifier 2O 3/ Al 2O 3Catalyst, the oxide that makes after drying and the roasting with Zn, Mn or rare earth element is the Cr of modifier 2O 3/ Al 2O 3Catalyst;
(4) contain the Cr of two kinds of oxide modifiers 2O 3/ Al 2O 3Preparation of catalysts is undertaken by step impregnation method.
3, according to the described chromium-based catalysts of claim 2 in the application from synthesis gas and the direct synthesizing low-carbon amine of ammonia, the catalyst sintering temperature after it is characterized in that flooding is 300～800 ℃.
4, according to the described chromium-based catalysts of claim 1 in the application from synthesis gas and the direct synthesizing low-carbon amine of ammonia, it is characterized in that:
Reacting gas is the gaseous mixture of synthesis gas and ammonia, wherein CO in the synthesis gas: H 2=1: 0.5～1: 5 volume ratios, and CO: NH 3=1: 0.1～1: 10 volume ratios; The ratio that the gaseous mixture of synthesis gas and ammonia accounts for overall reaction gas is 5%～100% volume fraction, and balanced gas is H 2Or N 2
Reaction condition is: 200～600 ℃ of reaction temperatures, and reaction pressure normal pressure～10Mpa, the ammonia air speed is 10～10000h -1
5, according to the described chromium-based catalysts of claim 4 in the application from synthesis gas and the direct synthesizing low-carbon amine of ammonia, it is characterized in that:
Catalyst was used H before reaction 2Or H 2Reduce H with the gaseous mixture of Ar 2/ Ar=5: 95～50: 50 volume ratios; Reducing condition is: 200～600 ℃ of reduction temperatures, 0.5～8 hour recovery time.
CNB001233629A 2000-12-06 2000-12-06 Cr-base catalyst for synthesizing low-carbon amines directly from synthetic gas and ammonia gas and its application Expired - Fee Related CN1180882C (en)

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