CN106925257A - A kind of preparation method that isobutanol dispersed catalysts are prepared by synthesis gas - Google Patents
A kind of preparation method that isobutanol dispersed catalysts are prepared by synthesis gas Download PDFInfo
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- CN106925257A CN106925257A CN201710210150.9A CN201710210150A CN106925257A CN 106925257 A CN106925257 A CN 106925257A CN 201710210150 A CN201710210150 A CN 201710210150A CN 106925257 A CN106925257 A CN 106925257A
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- isobutanol
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
- C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
- C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
A kind of preparation method of synthesis gas isobutanol high-dispersion loading type catalyst, comprises the following steps：Multi-walled carbon nano-tubes disperses dense HNO3In, it is heated to reflux, obtain solution A；Solution A is filtered, is washed, the carbon pipe handled well；By the Zn (NO of formula ratio3)2、Cr(NO3)3、KNO3The interior of enough ethanol is dissolved in, solution B is obtained；The carbon pipe that will be handled well is added in solution B, carries out ultrasonically treated under stirring, obtains gluey presoma C；Dry presoma C；By dried presoma C in N2It is calcined under atmosphere, obtains solid particle；By solid particle grind into powder, compressing tablet obtains isobutanol high-dispersion loading type catalyst to 30 ~ 40 mesh.360 ~ 420oC, 3 ~ 12MPa, 2000 ~ 15000h‑1, H2/CO：Under 1 ~ 3 reaction condition, the selectivity of catalyst prepared by the present invention to isobutanol.
Description
Technical field
The invention belongs to catalyst technical field, and in particular to a kind of to prepare isobutanol dispersed catalysts by synthesis gas
Preparation method.
Background technology
Isobutanol also known as dimethyl propyl alcohol, are a kind of basic organic chemical industry raw materials, and isobutanol was put into 2010
Environmental Protection Agency's fuel additive catalogue, it is also possible to mix to reduce the numerical value of PM 2.5 in air with diesel oil, can also add aviation
Fuel oil, its application field and application prospect are extremely wide.
Synthesizing isobutyl alcohol catalyst by synthesis gas mainly has two classes：Zn-Cr bases catalyst and the alkali gold of alkali metals modified
The modified Cu-Zr base catalyst of category；Also the pure Zr bases catalyst preparation isobutanol of someone's alkali metals modified in recent years.Cu-Zr
Base catalyst reaction condition is more gentle（6~8 Mpa, 350~380℃）But product composition is complicated so that cost for purification is significantly
Increase；Zn-Cr base catalyst reactions condition is harsh（10~12 Mpa, 400~420℃）, but product composition is simple（Methyl alcohol with
Isobutanol accounts for the 95% of alcohol phase component）, purification of products cost can be reduced and people's attention is increasingly subject to.
Forefathers prepare Zn-Cr base catalyst using coprecipitation mostly, and the specific surface area of catalyst of preparation is smaller, causes to urge
Agent activity is relatively low, accessory substance CO2It is larger with alkane growing amount.
The content of the invention
In order to overcome the above-mentioned deficiency of prior art, isobutanol load is prepared it is an object of the invention to provide a kind of synthesis gas
The preparation method of type catalyst.The present invention supports Zn-Cr base catalyst with CNTs, obtains active sites in CNT inside wall height
The good catalyst system of dispersion, carrier and active component synergy, to improve the activity and selectivity of catalyst, reduces
Accessory substance CO2Generation.The present invention solves that catalyst activity obtained in prior art is low, poor selectivity, asking more than side reaction
Topic.
To achieve these goals, the technical solution adopted in the present invention is：A kind of synthesis gas isobutanol high dispersive is born
The preparation method of supported catalyst, with multi-walled carbon nano-tubes as raw material, preprocessed, ultrasonic, drying, roasting obtain gas system different
Butanol high-dispersion loading type catalyst, step specific as follows：
1）Take 1 mass parts multi-walled carbon nano-tubes be scattered in 15 ~ 30 mass parts 68 wt.% dense HNO3In, stirring, 100 ~
10 ~ 18 h are heated to reflux at 140 DEG C, solution A is obtained；
2）Solution A is filtered, is 7, the carbon pipe handled well by Washing of Filter Cake to filtrate PH；
3）By the Zn (NO of formula ratio3)2、Cr(NO3)3、KNO3The interior of enough ethanol is dissolved in, solution B is obtained；
4）The step of taking 1 mass parts 2）The carbon pipe handled well is added in the solution B of 20 ~ 40 mass parts, and ultrasound is carried out under stirring
Treatment, obtains gluey presoma C；
5）By presoma C in 110 ~ 130 DEG C of 8 ~ 15h of drying；
6）By step 5）Dried presoma C is in N2In 350 ~ 700 DEG C under atmosphere, the h of the h of roasting time 4 to 8 obtain solid
Particle；
7）By step 6）The solid particle grind into powder for obtaining, compressing tablet is standby to 30 ~ 40 mesh, obtains isobutanol high-dispersion load
Type catalyst.
The step 1）Middle carbon bore is 4 ~ 8 nm, and external diameter is 10 ~ 20 nm.
The step 3）Middle Zn (NO3)2、Cr(NO3)3、KNO3Mol ratio formula be：
Zn(NO3)2 5 ~ 15 parts；
Cr(NO3)3 5 ~ 15 parts；
KNO3 1 ~ 5 part.
The step 4）The time of middle ultrasonic immersing is 8 ~ 15h.
The step 6）Middle 2 DEG C/min of temperature rise period heating rate.
The beneficial effects of the invention are as follows：
In reaction temperature：360~420oC, reaction pressure：3 ~ 12 MPa, reaction velocity：2000~15000 h-1, H2/CO：1~3
Reaction condition under, the catalyst selectivity with preferable reactivity worth, alcohol prepared by the present invention can reach 50%, isobutyl
The selectivity of alcohol is 25%, alkane and CO2Selectivity it is relatively low.Preparation method rational technology of the present invention, prepares simply, and raw material is easy
Obtain inexpensively.Catalyst prepared by the present invention has preferable selectivity, accessory substance alkane and CO to product isobutanol2Selectivity compared with
It is low.
Specific embodiment
Principle of the invention and feature are described below, example is served only for explaining the present invention, is not intended to limit
The scope of the present invention processed.
Embodiment 1
20.9 g carbon bores are taken for 4 nm, external diameter is the multi-walled carbon nano-tubes of 10 nm, is placed in and fills the wt.% of 300.5 g 68
HNO3There-necked flask in, flow back 10 h at 100 DEG C, obtains solution A.Solution A is filtered, is washed with deionized water
It is 7, the carbon pipe handled well to PH.Take a certain amount of Zn (NO3)2、Cr(NO3)3、KNO3, it is dissolved in the excess ethyl alcohol in beaker
It is interior, it is completely dissolved, solution B is denoted as, 5 parts of Zn (NO are contained in every part of solution B3)2, 5 parts of Cr (NO3)3And 1 part of KNO3.Take
The carbon pipe that 15.4 g are handled well is added in 300.5 g solution Bs, and ultrasonically treated 10 h is carried out under stirring, obtains gluey presoma
C.Presoma C is put into baking oven and is dried, drying temperature is 130 DEG C, drying time is 15 h.Dried presoma is in N2Atmosphere
In 2 DEG C/min of heating rate in tube furnace under enclosing, sintering temperature is 7 DEG C, the h of roasting time 4.By solid particle grind into powder,
Compressing tablet is standby to 30 ~ 40 mesh, obtains 18.3 g products.
Embodiment 2
20.8 g carbon bores are taken for 8 nm, external diameter is the multi-walled carbon nano-tubes of 20 nm, is placed in and fills the wt.% of 600.3 g 68
HNO3There-necked flask in, flow back 18 h at 140 DEG C, obtains solution A.Solution A is filtered, is washed with deionized water
It is 7, the carbon pipe handled well to PH.Take a certain amount of Zn (NO3)2、Cr(NO3)3、KNO3, it is dissolved in the excess ethyl alcohol in beaker
It is interior, it is completely dissolved, solution B is denoted as, 15 parts of Zn (NO are contained in every part of solution B3)2, 15 parts of Cr (NO3)3And 5 parts of KNO3.Take
The carbon pipe that 15.9 g are handled well is added in 639.9 g solution Bs, and ultrasonically treated 10 h is carried out under stirring, obtains gluey presoma
C.Presoma C is put into baking oven and is dried, drying temperature is 130 DEG C, drying time is 15 h.Dried presoma is in N2Atmosphere
In 2 DEG C/min of heating rate in tube furnace under enclosing, sintering temperature is 700 DEG C, the h of roasting time 8.Solid particle is pulverized
End, compressing tablet is standby to 30 ~ 40 mesh, obtains 19.7 g products.
Embodiment 3
20.4 g carbon bores are taken for 6 nm, external diameter is the multi-walled carbon nano-tubes of 15 nm, is placed in and fills the wt.% of 450.8 g 68
HNO3There-necked flask in, flow back 12 h at 120 DEG C, obtains solution A.Solution A is filtered, is washed with deionized water
It is 7, the carbon pipe handled well to PH.Take a certain amount of Zn (NO3)2、Cr(NO3)3, in the excess ethyl alcohol that is dissolved in beaker, make
It is completely dissolved, and is denoted as solution B, and 12 parts of Zn (NO are contained in every part of solution B3)2, 10 parts of Cr (NO3)3And 3 parts of KNO3.Take 15.6g
The carbon pipe handled well is added in 498.4 g solution Bs, and ultrasonically treated 10 h is carried out under stirring, obtains gluey presoma C.Will be preceding
Drive body C is put into baking oven and dries, and drying temperature is 110 DEG C, and drying time is 8 h.Dried presoma is in N2Under atmosphere in
2 DEG C/min of heating rate in tube furnace, sintering temperature is 400 DEG C, the h of roasting time 6.By solid particle grind into powder, compressing tablet
It is standby to 30 ~ 40 mesh, obtain 17.6 g products.
Embodiment 4
The catalyst for taking the preparation of 3 ~ 5 ml embodiments 1 ~ 3 loads fixed bed reactors（Φ15×48）, in 10% H2/N2（Volume
Than）Also temperature programming to 400 is carried out in Primordial Qi atmosphere by certain proceduresoC, reduces 4 hours, switches to synthesis gas, boosts to institute
Pressure is needed to be tested.Synthesis gas enters reactor after being measured through mass flowmenter, is reacted under required reaction temperature.Instead
Answer condition：Reaction temperature：400 DEG C, reaction pressure：10MPa, reaction velocity：3000 h-1, H2/CO：1~3.
Reacted gas componant and content are measured with GC-MS, obtains the catalyst of the preparation of embodiment 1 ~ 3 to urging
Agent is to fusel, isobutanol, miscellaneous hydrocarbon and CO2Selectivity evaluation result, test result is as shown in table 1：
Above test result shows, in 400 DEG C, 10MPa, 3000 h-1Under reaction condition, catalyst prepared by the present invention has
Preferable reactivity worth, the selectivity to fusel can reach 35% or so, and isobutanol is selectively 15% or so, CO2Selection
Property is relatively low.
Present pre-ferred embodiments are the foregoing is only, is not intended to limit the invention, it is all in spirit of the invention and former
Within then, any modification, the equivalent made, improve etc., should all be included within protection scope of the present invention.
Claims (5)
1. a kind of preparation method of synthesis gas isobutanol high-dispersion loading type catalyst, with multi-walled carbon nano-tubes as raw material, passes through
Pretreatment, ultrasound, drying, roasting, obtain gas isobutanol high-dispersion loading type catalyst, it is characterised in that including following step
Suddenly：
1）Take 1 mass parts multi-walled carbon nano-tubes be scattered in 8 ~ 9 mass parts 68 wt.% dense HNO3In, stirring, 100 ~ 140
10 ~ 18 h are heated to reflux at DEG C, solution A is obtained；
2）Solution A is filtered, is 7, the carbon pipe handled well by Washing of Filter Cake to filtrate PH；
3）By the Zn (NO of formula ratio3)2、Cr(NO3)3、KNO3The interior of enough ethanol is dissolved in, solution B is obtained；
4）The step of taking 1 mass parts 2）The carbon pipe handled well is added in the solution B of 5 ~ 35 mass parts, and ultrasonic place is carried out under stirring
Reason, obtains gluey presoma C；
5）By presoma C in 110 ~ 130 DEG C of 8 ~ 15h of drying；
6）By step 5）Dried presoma C is in N2In 350 ~ 700 DEG C under atmosphere, the h of the h of roasting time 4 to 8 obtain solid
Grain；
7）By step 6）The solid particle grind into powder for obtaining, compressing tablet is standby to 30 ~ 40 mesh, obtains isobutanol high-dispersion load
Type catalyst.
2. the preparation method of a kind of synthesis gas isobutanol high-dispersion loading type catalyst according to claims 1, its
It is characterised by, the step 1）Middle carbon bore is 4 ~ 8 nm, and external diameter is 10 ~ 20 nm.
3. the preparation method of a kind of synthesis gas isobutanol high-dispersion loading type catalyst according to claims 1, its
It is characterised by, the step 3）Middle Zn (NO3)2、Cr(NO3)3、KNO3Mol ratio formula be：
Zn(NO3)2 5 ~ 15 parts；
Cr(NO3)3 5 ~ 15 parts；
KNO3 1 ~ 5 part.
4. the preparation method of a kind of synthesis gas isobutanol high-dispersion loading type catalyst according to claims 1, its
It is characterised by, the step 4）The time of middle ultrasonic immersing is 8 ~ 15h.
5. the preparation method of a kind of synthesis gas isobutanol high-dispersion loading type catalyst according to claims 1, its
It is characterised by, the step 6）Middle 2 DEG C/min of temperature rise period heating rate.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3524317C2 (en) * | 1985-07-08 | 1989-10-26 | Union Rheinische Braunkohlen Kraftstoff Ag, 5000 Koeln, De | |
| US5770541A (en) * | 1995-12-08 | 1998-06-23 | Exxon Research And Engineering Company | Isobutanol synthesis catalyst |
| CN1669649A (en) * | 2004-12-31 | 2005-09-21 | 厦门大学 | Promoting cobalt-copper base catalyst for preparation of low carbon mixed alcohol-carbon nano tube from synthetic gas and preparing method thereof |
| CN103252238A (en) * | 2013-05-17 | 2013-08-21 | 浙江大学 | Catalyst for selectively synthesizing gasoline and diesel components by synthesis gas and preparation method of catalyst |
| CN106540680A (en) * | 2015-09-22 | 2017-03-29 | 中国石油化工股份有限公司 | Catalyst for synthesis gas isobutanol and application thereof |
-
2017
- 2017-03-31 CN CN201710210150.9A patent/CN106925257A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3524317C2 (en) * | 1985-07-08 | 1989-10-26 | Union Rheinische Braunkohlen Kraftstoff Ag, 5000 Koeln, De | |
| US5770541A (en) * | 1995-12-08 | 1998-06-23 | Exxon Research And Engineering Company | Isobutanol synthesis catalyst |
| CN1669649A (en) * | 2004-12-31 | 2005-09-21 | 厦门大学 | Promoting cobalt-copper base catalyst for preparation of low carbon mixed alcohol-carbon nano tube from synthetic gas and preparing method thereof |
| CN103252238A (en) * | 2013-05-17 | 2013-08-21 | 浙江大学 | Catalyst for selectively synthesizing gasoline and diesel components by synthesis gas and preparation method of catalyst |
| CN106540680A (en) * | 2015-09-22 | 2017-03-29 | 中国石油化工股份有限公司 | Catalyst for synthesis gas isobutanol and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| PENG WANG ET AL.: ""Effect of the promoter and support on cobalt-based catalysts for higher alcohols synthesis through CO hydrogenation"", 《FUEL》 * |
| SHAOPENG TIAN ET AL.: ""The role of potassium promoter in isobutanol synthesis over Zn-Cr based catalysts"", 《CATALYSIS SCIENCE & TECHNOLOGY》 * |
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