CN106423201A - Method for preparing TiO2-loaded rhodium-based catalyst of ethyl alcohol through acetic acid hydrogenation method - Google Patents
Method for preparing TiO2-loaded rhodium-based catalyst of ethyl alcohol through acetic acid hydrogenation method Download PDFInfo
- Publication number
- CN106423201A CN106423201A CN201610822253.6A CN201610822253A CN106423201A CN 106423201 A CN106423201 A CN 106423201A CN 201610822253 A CN201610822253 A CN 201610822253A CN 106423201 A CN106423201 A CN 106423201A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- preparation
- rhodium
- acetic acid
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/60—Platinum group metals with zinc, cadmium or mercury
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
-
- 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
- C07C29/132—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 an oxygen containing functional group
- C07C29/136—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—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 an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a method for preparing a TiO2-loaded rhodium-based catalyst of ethyl alcohol through an acetic acid hydrogenation method. Titanium dioxide serves as a carrier, rhodium or a rhodium oxide serves as a main catalyst, and metal or an oxide of the metal serves as an auxiliary catalyst. The preparation method is a deposition-precipitation method including the steps that an alkaline solution is added dropwise into a mixed solution composed of rhodium and M salt to form precipitate, then the carrier, namely titanium dioxide, is added and evenly stirred for a certain period of time, and precipitate matter is adsorbed on the carrier, namely titanium dioxide; then the product is filtered and washed to filter away impurities therein; drying and sintering are conducted to obtain a titanium-dioxide-loaded metal oxide. A hydrogenation reaction is conducted in a tubular fixed bed reactor, the catalyst is reduced in a reductive atmosphere, and a high conversion rate and selectivity can be obtained by controlling temperature, pressure, volume space velocity, hydrogen-acid ratio and other parameters of the reaction. The preparation method is simple, repeatability is high, the catalytic effect is good, and the catalyst is an ideal industrial catalyst for preparing ethyl alcohol through an acetic acid hydrogenation method.
Description
Technical field
The present invention relates to a kind of preparation method of catalyst and in particular to a kind of acetic acid preparation of ethanol by hydrogenating TiO2 load
Rhodium base catalyst and preparation method, belong to chemical catalyst preparing technical field.
Background technology
Ethanol is important large chemical products, is widely used in the fields such as food, medicine, new material, chemical industry, or reason
The free of contamination vehicle fuel of high-octane rating thought and its additive.Ethanol can be deployed into alcohol fuel after adding denaturant, adds
It is added on the fuel being used as automobile in automobile, greatly reduce the pollution to environment during gasoline combustion.
The primary synthetic methods of ethanol have biological fermentation process and chemical synthesiss.One of biological fermentation process raw material is various grains
Food crop, but the problems such as there is " striving grain with the people, strive ground with grain ", therefore country is controlled to grain alcohol.Non- grain second
The alcohol either secondary cellulosic ethanol technology still 1.5 Replacing fuel ethanol technology with Maninot esculenta crantz., Radix Ipomoeae and sugar grass etc. as raw material,
Because being limited by technology itself and the restriction of raw material, cost remains high, and the level of profitability is general.
Chemical synthesiss ethanol mainly has ethylene hydration method, synthesis gas direct synthesis technique, acetic acid hydrogenation method etc..
Ethylene hydration method mainly adopts the ethylene of petroleum refining to react with water for raw material, generates under acid catalyst effect
Ethanol.This method is subject to the fluctuation of ethylene price larger, and catalyst is generally inorganic acids it is desirable to equipment has acidproof resistance to pressure
Can, higher to equipment requirements.
Synthesis gas direct synthesis technique mainly becomes ethanol with synthesis gas for raw material one-step conversion.But current synthesis gas system
Standby method conversion ratio is relatively low, and target product ethanol selectivity is too poor, and by-product is more, separates difficult.
Acetic acid hydrogenation method is with acetic acid as raw material, generates the ethanol of corresponding carbon number by hydrogen addition technology.Acetic acid is to be with coal
Raw material prepares through synthesising gas systeming carbinol, then methanol carbonyl.China's acetic acid plant production capacity in 2015 more than 10,000,000 tons,
About 6,000,000 tons of annual production, production capacity is seriously superfluous, downstream the large-scale development of product and using imperative.China's grain produces
Amount is not abundant, and petroleum resources are rare, rich coal resources, and the exploitation technology path through acetic acid ethanol for the coal resources is to coal
The clean utilization of resource and minimizing open new approach to the dependence of petroleum resources, raising Chinese energy safety are had important
Strategic importance and profound influence.
Acetic acid directed hydrogenation refers to that acetic acid is directly reacted with hydrogen for raw material, in certain temperature, pressure, specifically urges
Ethanol is prepared under agent.All have been reported that both at home and abroad, such as United States Patent (USP) US20130178664A1, US20130178668A1 and
It is major catalyst that US20140128642A1 discloses using Pt, Co and/or Sn is promoter, in W, Mo, Nb, V, Ta
Plant or multiple modified SiO2For carrier, using the catalyst of infusion process preparation, acetic acid conversion ratio is more than 20%.
Chinese patent CN201210057568.8 is open to use Pt-Ag catalyst, CN201210575776.7 and
CN201310129903.5 is open to use Pd-Cu catalyst, and CN201210366143.5 is open to use Pt-Sn catalyst,
The open bimetallic catalyst using PtRu composition of CN201210575780.3, CN201310129902.0 is open to be urged using Pt base
Agent etc. is applied to acetic acid direct hydrogenation ethanol system.
Therefore the major catalyst great majority of acetic acid preparation of ethanol by hydrogenating are various noble metal catalysts, promoter is each
Plant one or more of transition metal or alkali metal, carrier mostly is various types of metal-oxides or other types of porous
Material.But the catalytic effect of catalyst is not highly desirable, have such problems as that conversion ratio is not high enough or selectivity is poor.
Above-mentioned all document heres quote in full to make reference.
Content of the invention
Subject matter to be solved by this invention is that the catalyst of prior art preparation is applied to acetic acid preparation of ethanol through hydrogenation
There is a problem of that conversion ratio and selectivity are relatively low, the rhodium base catalysis that a kind of TiO2 of new acetic acid preparation of ethanol by hydrogenating loads is provided
The preparation method of agent.Described catalyst is with titanium dioxide as carrier, with the oxide of rhodium or rhodium as major catalyst, with metal
Or its oxide is promoter, the method is simple, repeatable by force, be easily achieved industrialization.
Realize above-mentioned purpose to employ the following technical solutions：
A kind of acetic acid direct hydrogenation prepares the preparation method of the rhodium base catalyst of ethanol, and the method is with titanium dioxide for carrying
Body, adds major catalyst, promoter, prepares rhodium base catalyst using deposition-precipitation method, its preparation method includes following successively
Step：
(1) preparation of metal salt solution：Weigh rhodium salt by weight, and be added thereto to M salt by weight proportion, be made into
Metal salt solution；
(2) preparation of aqueous slkali：Weigh one or more alkali by weight and be configured to the alkali soluble that concentration is 5%-40%
Liquid；
(3) at 30-100 DEG C of arbitrary temperature, aqueous slkali is added drop-wise in metal salt solution and is precipitated, until terminal
PH value be 6-9 between till, be subsequently adding the titanium dioxide of 20-60g weight, be sufficiently stirred for 1-8 hour make deposit adsorb
On carrier titanium dioxide, obtain quasi- catalyst；
(4) by prepared quasi- catalyst filtration in step (3), filter impurity therein, and wash with water, Ran Hougan
Dry, obtain the catalyst of titanium dichloride load；
(5) by the catalyst prepared by step (4), under 300-700 DEG C of high temperature, roasting 1-24 hour obtains metallic state
Rh-M base catalyst is used for acetic acid and is hydrogenated with.
Preferably, Rh base catalyst is major catalyst, and major catalyst active component is with the oxide shape of rhodium or rhodium
Formula is contained therein.
Preferably, select one or more metal M and do promoter, promoter is aoxidized with metal or its metal
In wherein presented in thing, promoter is used for improving the performance of major catalyst Rh.
Preferably, in Rh-M catalyst, the mass fraction of Rh is between 0.1-10, and the mass fraction of M salt is 0.1-
Between 10, the mass fraction of titanium dioxide is between 80-99.8.
Preferably, described M salt is Ni, one or more of Cu, La, Mo, Mn, Fe, Co, Zn, Sn, Zr salt
Mixing.
Preferably, described rhodium salt and M salt are any one or more in nitrate, chlorate or acetate
Mixing.
Preferably, the mol ratio of described rhodium salt and M salt is 0.1-10：Any number in 1.
Preferably, described carrier is titanium dioxide, and its crystal formation is Detitanium-ore-type, rutile-type or two kinds of crystal formations
The mixing of one or more of mixed type.
Preferably, described alkali is ammonia, carbamide, ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide, sodium carbonate, carbonic acid
One or more of hydrogen sodium, potassium hydroxide, potassium carbonate, potassium bicarbonate mix.
Preferably, the M of Rh-M catalyst is the general designation of various metals catalyst.
Using technique scheme, compared with prior art, aqueous slkali is added drop-wise to rhodium and/or M salt composition by the present invention
Form precipitation in mixed solution, be then added thereto to titanium dioxide, uniform stirring adsorbs deposit in carrier titanium dioxide
On titanium；Then filtration washing is to filter impurity therein；Metal-oxide dry, that roasting obtains titanium dichloride load；By this
Catalyst reduces in reducing atmosphere, and the rhodium base catalyst obtaining metallic state is used for acetic acid hydrogenation.Hydrogenation reaction is solid in tubular type
Carry out in fixed bed reactor, by control react temperature, pressure, volume space velocity, hydracid than etc. parameter obtain higher conversion
Rate and selectivity.The present invention selectes with Rh base catalyst as major catalyst, disclosure satisfy that the realization of acetic acid hydrogenation, selectes another kind
Or various metals M does promoter, M is Ni, one or more of Cu, La, Mo, Mn, Fe, Co, Zn, Sn, Zr.Selected dioxy
Change titanium is carrier, is because the thermal and magnetic of titanium dioxide, light-sensitive characteristic and surface stability etc. are different from conventional carrier.This
The bright Rh-M catalyst preparing titanium dichloride load, preparation process is simple, repeatable strong, excellent catalytic effect, and prepared urges
Agent is applied to there is stronger practical significance in commercial production.
Specific embodiment
Below by specific embodiment, the present invention is further explained in detail.
The invention discloses a kind of acetic acid preparation of ethanol by hydrogenating TiO2 load rhodium base catalyst and preparation method and its should
With described acetic acid hydrogenation catalyst is actually three component catalysts, including catalyst activity component Rh, promoter
M and carrier titanium dioxide.Wherein promoter M can be used to improve the performance of major catalyst Rh, above-mentioned three component synergism
The performance of catalyst is made to be significantly improved.
Major catalyst active component of the present invention is contained therein with the oxide form of rhodium or rhodium.Promoter with metal or
In wherein presented in its metal-oxide.
In the Rh-M catalyst of titanium dichloride load of the present invention, the mass fraction of Rh is that between 0.1-10, the quality of M salt is divided
Number is (containing endpoint value) between 0.1-10, and the mass fraction of titanium dioxide is between 80-99.8 (containing endpoint value).
M salt is Ni, one or more of Cu, La, Mo, Mn, Fe, Co, Zn, Sn, Zr salt；Rhodium salt and M salt can be it
Any one or more in nitrate, chlorate or acetate.The mol ratio of rhodium salt and M salt can be (0.1-10)：In 1
Any number.
The crystal formation of titanium dioxide is any one in the mixed type of Detitanium-ore-type, rutile-type or two kinds of crystal formations or many
Kind.
Weigh one or more alkali by weight and be configured to the aqueous slkali that concentration is 0.2-2.0mol/L；Alkali be ammonia,
In carbamide, ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate one
Plant or multiple.
The M of Rh-M catalyst is the general designation of various metals catalyst.
Acetic acid preparation of ethanol by hydrogenating catalyst of the present invention is preferably used in acetic acid hydrogenation ethanol production, but is not excluded for for other
Organic acid hydrogenation is produced in the reaction of other products.When this catalyst is used for the reaction of acetic acid preparation of ethanol by hydrogenating, reaction temperature
For 200-350 DEG C, pressure is 1-8MPa, and the air speed of acetic acid is 0.5-3/ hour, and hydracid ratio is under the reaction condition for 10-200, vinegar
The conversion ratio of acid is more than 60%, and the selectivity of ethanol is more than 85%.
Concrete preparation method embodiment：
Embodiment 1
Weigh 1g radium chloride (III) hydrate, 0.5g cabaltous nitrate hexahydrate, be made into 100mL slaine in volumetric flask
Aqueous solution.In the environment of 40 DEG C to the aqueous solution of slaine in add 25-28% ammonia until endpoint pH be 7.5；To
Add 20g anatase titanium dioxide in solution and continue to stir 4 hours and make precipitation adsorption on carrier titanium dioxide, obtain standard
Catalyst；Then by quasi- catalyst filtration to filter impurity therein, and wash with water, be dried 12 in the environment of 100 DEG C little
When, obtain catalyst；Take out catalyst in Muffle kiln roasting, from room temperature with the ramp of 10 DEG C/min to 400 DEG C, and protect
Hold roasting in 4 hours, be then slowly dropped to room temperature and obtain Rh-M rhodium base catalyst, referred to as Cat-1.
Embodiment 2
Weigh 1.0g rhodium acetate (II) dimer, 2g acetic acid molybdenum, 2g nickel nitrate is made into the water of 1L slaine in volumetric flask
Solution, is placed in large beaker.In the environment of 80 DEG C to the aqueous solution of slaine in add 1.0mol/L sodium hydroxide water-soluble
Liquid is until endpoint pH is 6.5；Add 50g rutile titanium dioxide and continue to stir 4 hours and make precipitation adsorption in solution
On carrier titanium dioxide, obtain quasi- catalyst；Then by quasi- catalyst filtration, filter impurity therein, and wash with water, in
In the environment of 120 DEG C, drying obtains catalyst in 8 hours；Take out catalyst in Muffle kiln roasting, from room temperature with the speed of 5 DEG C/min
Rate is warming up to 550 DEG C, and keeps 8h roasting, and then slow cooling, to room temperature, obtains Rh-M catalyst, referred to as Cat-2.
Embodiment 3
Weigh 0.5g radium chloride (III) hydrate, 2.0g tetra- is hydrated manganese acetate, in the volumetric flask of 1000mL, is joined
Make metal salt solution.In the environment of 60 DEG C to the aqueous solution of slaine in add 1.0mol/L aqueous sodium carbonate until
Endpoint pH is 8.0；Add the titanium dioxide of 50g Detitanium-ore-type and rutile-type mixing and continue to stir 6 hours in solution
Make precipitation adsorption on carrier titanium dioxide, obtain quasi- catalyst；Then by quasi- catalyst filtration, filter impurity therein, and
Wash with water, drying under dry environment at 120 DEG C obtains catalyst in 10 hours；Take out catalyst in Muffle kiln roasting, from
Room temperature and keeps 10h roasting with the ramp of 5 DEG C/min to 650 DEG C；Then slow cooling, to room temperature, obtains Rh-M catalysis
Agent, referred to as Cat-3.
Embodiment 4
Weigh 0.5g rhodium acetate (II) dimer, 1.0g acetic acid zirconium, 1.0g zinc acetate in the volumetric flask of 1000mL, by it
It is made into metal salt solution.In the environment of 60 DEG C to the aqueous solution of slaine in add 1.0mol/L aqueous sodium carbonate until
Endpoint pH is 7.0；Add the titanium dioxide of 50g Detitanium-ore-type and rutile-type mixing and continue to stir 6 hours in solution
Make precipitation adsorption on carrier titanium dioxide, obtain quasi- catalyst；Then quasi- catalyst filtration, to filter impurity therein, and
Wash with water, be dried 10 hours in the environment of 120 DEG C, obtain catalyst.Take out catalyst in Muffle kiln roasting, from room temperature
With the ramp of 5 DEG C/min to 350 DEG C, and keep 10h roasting.Then slow cooling, to room temperature, obtains Rh-M catalyst, claims
For Cat-4.
Test case
Obtained catalyst in above-described embodiment 1-4 is used in the reaction of acetic acid gas phase hydrogenation ethanol, and investigates
The catalytic performance of above-mentioned catalyst.
The reduction of above-mentioned catalyst and evaluation procedure are carried out on the laboratory scale tubular fixed-bed reactor of 10mL.
With quartz sand, catalyst is fixed on the constant temperature zone of reactor.Reduced using a certain proportion of nitrogen and hydrogen mixture, reduced journey
Sequence is to start to 100-400 DEG C of reduction temperature and to maintain certain time with the ramp of 5 DEG C/min from room temperature, afterwards slow homoiothermic
To reaction temperature, system pressure is risen to reaction pressure with pure hydrogen simultaneously.
Acetic acid is pumped into by liquid feedstock, and is vaporized, then send into reactor, the air speed of acetic acid after mixing with hydrogen
For 0.5-3.0/ hour, hydracid mol ratio is 10-200.After reaction, system condensation water cooling, is carried out point using gas-liquid separator
From liquid is collected in wet tank, takes out condensed product liquid at set intervals, with its product of gas chromatographic analysiss
Composition, and calculate the conversion ratio of acetic acid and the selectivity of ethanol according to area normalization method.The wherein conversion ratio of acetic acid and ethanol
Selectivity calculate according to the following formula：
The peak area of the conversion ratio of acetic acid=all products/(peak area of the peak area+acetic acid of all products) ×
100%.
Peak area × 100% of the peak area of the selectivity=ethanol of ethanol/all products.
Reaction result see table：
It should be noted that：The description of above example is only used for making the those of ordinary skill of technical field of the present invention
The principle of the present invention and marrow can be more clearly understood from it is not intended to any type of restriction is carried out to the present invention.
Claims (10)
1. a kind of TiO of acetic acid preparation of ethanol by hydrogenating2The preparation method of the rhodium base catalyst of load is it is characterised in that the method is with two
Titanium oxide be carrier, add major catalyst, promoter, rhodium base catalyst is prepared using deposition-precipitation method, its preparation method according to
Secondary comprise the steps：
(1) preparation of metal salt solution：Weigh rhodium salt by weight, and be added thereto to M salt by weight proportion, be made into metal
Saline solution；
(2) preparation of aqueous slkali：Weigh one or more alkali by weight and be configured to the alkali soluble that concentration is 0.2-2.0mol/L
Liquid；
(3) at 30-100 DEG C of arbitrary temperature, aqueous slkali is added drop-wise in metal salt solution and is precipitated, until endpoint pH
Till between 6-9, it is subsequently adding the titanium dioxide of 20-60g weight, being sufficiently stirred for 1-8 hour makes deposit adsorb in load
On body titanium dioxide, obtain quasi- catalyst；
(4) by prepared quasi- catalyst filtration in step (3), filter impurity therein, and wash with water, be then dried, obtain
Catalyst to titanium dichloride load；
(5) by the catalyst prepared by step (4), under 300-700 DEG C of high temperature, roasting 1-24 hour obtains the Rh-M of metallic state
Base catalyst is used for acetic acid and is hydrogenated with.
2. the preparation method of the rhodium base catalyst of TiO2 load of a kind of acetic acid preparation of ethanol by hydrogenating according to claim 1,
It is characterized in that, Rh base catalyst is major catalyst, and major catalyst active component is present in it with the oxide form of rhodium or rhodium
In.
3. the preparation method of the rhodium base catalyst of TiO2 load of a kind of acetic acid preparation of ethanol by hydrogenating according to claim 1,
It is characterized in that, select one or more metal M and do promoter, promoter is deposited in the form of metal or its metal-oxide
It is wherein, promoter is used for improving the performance of major catalyst Rh.
4. the preparation method of the rhodium base catalyst of TiO2 load of a kind of acetic acid preparation of ethanol by hydrogenating according to claim 1,
It is characterized in that, in Rh-M catalyst, the mass fraction of Rh is between 0.1-10, and the mass fraction of M is dioxy between 0.1-10
The mass fraction changing titanium is between 80-99.8.
5. the preparation method of the rhodium base catalyst of TiO2 load of a kind of acetic acid preparation of ethanol by hydrogenating according to claim 1,
It is characterized in that, described M salt is Ni, the mixing of one or more of Cu, La, Mo, Mn, Fe, Co, Zn, Sn, Zr salt.
6. the preparation method of the rhodium base catalyst of TiO2 load of a kind of acetic acid preparation of ethanol by hydrogenating according to claim 1,
It is characterized in that, described rhodium salt and M salt are any one or more mixing in nitrate, chlorate or acetate.
7. the preparation method of the rhodium base catalyst of TiO2 load of a kind of acetic acid preparation of ethanol by hydrogenating according to claim 6,
It is characterized in that, the mol ratio of described rhodium salt and M salt is 0.1-10：Any number in 1.
8. the preparation method of the rhodium base catalyst of TiO2 load of a kind of acetic acid preparation of ethanol by hydrogenating according to claim 1,
It is characterized in that, described carrier titanium dioxide, its crystal formation is in the mixed type of Detitanium-ore-type, rutile-type or two kinds of crystal formations
Plant or multiple mixing.
9. the preparation method of the rhodium base catalyst of TiO2 load of a kind of acetic acid preparation of ethanol by hydrogenating according to claim 1,
It is characterized in that, described alkali is ammonia, carbamide, ammonium carbonate, ammonium hydrogen carbonate, sodium hydroxide, sodium carbonate, sodium bicarbonate, hydrogen-oxygen
Change the mixing of one or more of potassium, potassium carbonate, potassium bicarbonate.
10. the preparation method of the rhodium base catalyst of TiO2 load of a kind of acetic acid preparation of ethanol by hydrogenating according to claim 1,
It is characterized in that, the M of Rh-M catalyst is the general designation of various metals catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610822253.6A CN106423201A (en) | 2016-09-14 | 2016-09-14 | Method for preparing TiO2-loaded rhodium-based catalyst of ethyl alcohol through acetic acid hydrogenation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610822253.6A CN106423201A (en) | 2016-09-14 | 2016-09-14 | Method for preparing TiO2-loaded rhodium-based catalyst of ethyl alcohol through acetic acid hydrogenation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106423201A true CN106423201A (en) | 2017-02-22 |
Family
ID=58168924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610822253.6A Pending CN106423201A (en) | 2016-09-14 | 2016-09-14 | Method for preparing TiO2-loaded rhodium-based catalyst of ethyl alcohol through acetic acid hydrogenation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106423201A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773193A (en) * | 2019-09-25 | 2020-02-11 | 万华化学集团股份有限公司 | Supported gas-sensitive catalyst, preparation method and application thereof in menthone synthesis |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001046874A (en) * | 1999-08-17 | 2001-02-20 | Mitsubishi Chemicals Corp | Hydrogenating catalyst and production of alcohols from carboxylic acids using the same |
| CN102600842A (en) * | 2012-03-02 | 2012-07-25 | 山西盛驰科技有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic acid as well as preparation method and application thereof |
| WO2013119306A1 (en) * | 2012-02-10 | 2013-08-15 | Celanese International Corporation | A hydrogenation catalyst for converting a mixture comprising acetic acid and ethyl acetate to ethanol |
| CN103288596A (en) * | 2012-02-27 | 2013-09-11 | 中国科学院大连化学物理研究所 | Method for preparing monohydric alcohol or dihydric alcohol through organic acid hydrogenation |
| US20140121422A1 (en) * | 2012-10-26 | 2014-05-01 | Celanese International Corporation | Hydrogenation Reaction Conditions For Producing Ethanol |
| CN104138758A (en) * | 2013-05-08 | 2014-11-12 | 中国科学院大连化学物理研究所 | High selectivity carbon dioxide methanation catalyst and preparation method and application thereof |
-
2016
- 2016-09-14 CN CN201610822253.6A patent/CN106423201A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001046874A (en) * | 1999-08-17 | 2001-02-20 | Mitsubishi Chemicals Corp | Hydrogenating catalyst and production of alcohols from carboxylic acids using the same |
| WO2013119306A1 (en) * | 2012-02-10 | 2013-08-15 | Celanese International Corporation | A hydrogenation catalyst for converting a mixture comprising acetic acid and ethyl acetate to ethanol |
| CN103288596A (en) * | 2012-02-27 | 2013-09-11 | 中国科学院大连化学物理研究所 | Method for preparing monohydric alcohol or dihydric alcohol through organic acid hydrogenation |
| CN102600842A (en) * | 2012-03-02 | 2012-07-25 | 山西盛驰科技有限公司 | Catalyst for preparing ethanol through hydrogenation of acetic acid as well as preparation method and application thereof |
| US20140121422A1 (en) * | 2012-10-26 | 2014-05-01 | Celanese International Corporation | Hydrogenation Reaction Conditions For Producing Ethanol |
| CN104138758A (en) * | 2013-05-08 | 2014-11-12 | 中国科学院大连化学物理研究所 | High selectivity carbon dioxide methanation catalyst and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张金龙等: "《光催化》", 31 August 2012, 华东理工大学出版社有限公司 * |
| 朱洪法: "《催化剂载体制备及应用技术》", 31 October 2014 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110773193A (en) * | 2019-09-25 | 2020-02-11 | 万华化学集团股份有限公司 | Supported gas-sensitive catalyst, preparation method and application thereof in menthone synthesis |
| CN110773193B (en) * | 2019-09-25 | 2022-08-02 | 万华化学集团股份有限公司 | Supported gas-sensitive catalyst, preparation method and application thereof in menthone synthesis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106946894B (en) | Application of the Pd radicel duplex metal catalyst in HBIW catalytic hydrogenolytic cleavage | |
| CN102658165B (en) | Catalyst for preparing ethanol by acetic acid gas phase hydrogenation and preparation method thereof | |
| CN110975938A (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN110327933A (en) | Hydrogenation of carbon dioxide prepares catalyst of methanol and its preparation method and application | |
| CN110961110B (en) | Catalyst and application thereof in 2,3,6-trichloropyridine hydrodechlorination | |
| CN102151568A (en) | Catalyst for preparing ethylene glycol by dimethyl oxalate hydrogenation, and preparation and use thereof | |
| CN109126808A (en) | A kind of additive modification copper-based catalysts and preparation method and applications | |
| CN107774263B (en) | A kind of preparation method of catalst for synthesis of methanol | |
| CN108499564A (en) | Catalyst in a kind of building-up process of methyl glycollate and preparation method thereof, application | |
| CN111514938A (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN107899583A (en) | It is a kind of to prepare catalyst of ethanol and preparation method thereof for methyl methanol syngas | |
| CN110368949B (en) | GaFe-based catalyst for preparing low-carbon alcohol by CO hydrogenation, preparation method and application thereof | |
| CN104190417B (en) | Preparation method of ruthenium-based bimetallic catalyst for preparing cyclohexene by partial hydrogenation of benzene | |
| CN115254100A (en) | For CO 2 Preparation and application of metal oxide doped type monatomic catalyst for preparing ethanol by hydrogenation | |
| CN114029063B (en) | Catalyst for preparing methanol by carbon dioxide hydrogenation and preparation method thereof | |
| CN105435799A (en) | Catalyst for ethanol preparation by ethyl acetate hydrogenation and preparation method for catalyst | |
| CN106518619A (en) | Method for preparing ethyl alcohol by hydrogenation of acetate | |
| CN106423202A (en) | Preparation method of rhodium-ruthenium composite catalyst for preparing ethyl alcohol through acetic acid hydrogenation | |
| CN102911693B (en) | Fischer-Tropsch synthesis method by employing mixed catalyst | |
| CN111686740B (en) | Preparation method of methanol synthesis catalyst | |
| CN106423201A (en) | Method for preparing TiO2-loaded rhodium-based catalyst of ethyl alcohol through acetic acid hydrogenation method | |
| CN104230641A (en) | Production method of isopropyl benzene | |
| CN101428226A (en) | Selective hydrogenation catalyst for fine purification of p-benzene dicarboxylic acid | |
| CN102671673A (en) | Cobalt-base Fischer-Tropsch synthesis catalyst, and preparation method and application thereof | |
| CN102649746A (en) | Method for producing glycolic acid ester through adding hydrogen in oxalic ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170222 |
|
| RJ01 | Rejection of invention patent application after publication |