CN105664918B - Preparation method for quenching recovery gas catalyst for preparing alcohol - Google Patents
Preparation method for quenching recovery gas catalyst for preparing alcohol Download PDFInfo
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- 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
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- 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
- B01J23/28—Molybdenum
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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
- B01J23/38—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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with molybdenum
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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
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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
The present invention relates to a kind of preparation method for quenching recovery gas catalyst for preparing alcohol, including：After aluminum oxide, pore creating material and noble metal and/or metal oxide containing precious metals are mixed, material I is obtained, salpeter solution is added in material I, obtains material II, then material II is carried out to extruded moulding, roasting successively, obtain carrier；Four thio ammonium molybdate is dissolved in the water to obtain maceration extract I, chromic nitrate and potassium carbonate co-dissolve are obtained into maceration extract II in water, carrier is put into after maceration extract I stands, it will be put into maceration extract II and stand after the carrier drying after being impregnated by maceration extract I again, dry the carrier after being impregnated afterwards；Carrier after dipping is calcined 2~6 hours under 500~800 DEG C and inert atmosphere, obtains and reclaims gas catalyst for preparing alcohol for quenching.The preparation method that this is used for quenching recovery gas catalyst for preparing alcohol is simple, easy to operation, realizes industrialization, and low into production cost, and the catalyst activity for being advantageous to promote and obtain on a large scale is high, and stability is good.
Description
Technical field
The present invention relates to catalyst technical field, especially, is related to a kind of system for quenching recovery gas catalyst for preparing alcohol
Preparation Method.
Background technology
The energy is the important foundation resource of human social development.The most important energy in the world today be oil, natural gas with
And coal these three, but increasingly exhausting with oil and natural gas resource will switch through between coal, particularly coking coal resource
Turning to liquid fuel has boundless prospect.
Coking coal belongs to one kind of coal resources, and caused red-hot red Jiao is needed its quenching during high-temperature coking
The utilization of ability convenience in transport or progress next step after cooling.Existing quenching technology mainly includes dry coke quenching and coke wet quenching technology,
It can all be produced with H during the quenching of both technologies2、CO、CO2And CH4For the high-temperature flue gas of main component.However,
This part carbonaceous gas recovery is converted into alcohol liquid fuel to have very important significance to coking industry, while can also
To a certain extent alleviate China's energy scarcity phenomenon so that resource carry out effectively using and meet environmental protection will
Ask.In consideration of it, the key that the high-temperature flue gas during quenching is prepared into alcohol-based liquid is the research of catalyst.
At present, the Cu-Zn-Al systems for mainly having German Shandong strange that high-temperature flue gas is prepared into the catalyst of alcohol-based liquid urge
Agent and the Zn-Cr-K series catalysts of Italian Si Namu (Snam) company, both serial catalyst are to pass through addition
Obtained by alkali metal or Modified With Alkali-earth Compounds, although their activity preferably reaction condition more harshnesses, it is necessary to
High-temperature flue gas is prepared into alcohol-based liquid under conditions of 15~21MPa and 350~450 DEG C.In addition, France Petroleum Institute opens
Although the Cu-Co series catalysts reaction conditions of hair are gentle, less stable.
In addition, molybdenum sulfide catalyst is more and more closed due to its good sulfur resistance and higher selectivity
Note, the sulfur resistive MoS developed such as Dow Chemical company2Series catalysts, but high-temperature flue gas is being prepared into alcohol-based liquid
When, to H2There are strict requirements with CO charge ratio, simultaneously because CO can form carbonyl in Co and reaction raw materials in catalyst aid
Base cobalt, the stability of the catalyst and life-span can reduce.
Although the molybdenum system vulcanization hydrogen catalyst that Shanxi Inst. of Coal Chemistry, Chinese Academy of Sciences develops solves above-mentioned carried
And MoS2The shortcomings that series catalysts, but work as in reaction mass and a certain amount of CO be present2Or CH4When, can be to the activity of catalyst
Affect, while prepare compression molding method used in the catalyst and be difficult to industrialize.
The content of the invention
In order to solve the above problems, present inventor has performed studying with keen determination, as a result find：By the carrier being prepared successively
It is impregnated into the aqueous solution of four thio ammonium molybdate and the aqueous solution simultaneously containing chromic nitrate and potassium carbonate, obtains for quenching
Gas catalyst for preparing alcohol is reclaimed, higher, the stability height for quenching recovery gas catalyst for preparing alcohol activity being prepared by this method,
And preparation method is simple and convenient, cost is cheap, so as to complete the present invention.
It is an object of the invention to provide a kind of preparation method for quenching recovery gas catalyst for preparing alcohol, including following three
Individual step.
Step 1: after aluminum oxide, pore creating material and noble metal and/or metal oxide containing precious metals are mixed, material I is obtained, will
Salpeter solution is added in the material I, is preferably sprayed at salpeter solution in obtained material I, is obtained material II, then will
Resulting material II carries out extruded moulding, roasting successively, obtains carrier.
In above-mentioned steps one, one or more of the pore creating material in sesbania powder and flocking powder, wherein, sesbania powder
It can also be obtained with flocking powder by commercially available by making by oneself, at the same time, can be by actual demand to sesbania powder and plant
The particle diameter of suede powder is selected, and has no special demand.
In above-mentioned steps one, one kind in gold, silver, gallium, ruthenium, rhodium, palladium, osmium, iridium and platinum of the noble metal or
It is a variety of, it is preferable that one or more of the noble metal in gold, gallium and silver；The metal oxide containing precious metals are selected from gallium oxide
With the one or more in silver oxide.
In above-mentioned steps one, preferably the mass percent concentration of salpeter solution is 0.5~20%, it is further preferred that
The mass percent concentration of salpeter solution is 2.5~15%, it is further preferred that the mass percent concentration of salpeter solution is
5~12.5%, most preferably 8~10%.
In above-mentioned steps one, involved aluminum oxide, noble metal and metal oxide containing precious metals are both preferably powdered, when
During choice of powder shape, the size of particle diameter can be selected according to the actual requirements.
In above-mentioned steps one, the weight of aluminum oxide, the weight of pore creating material and noble metal and metal oxide containing precious metals it is total
The ratio of weight is preferably aluminum oxide：Pore creating material：Gross weight=10~45 of noble metal and metal oxide containing precious metals：0.5~5：0.3
~2, it is further preferred that the weight of aluminum oxide, the weight of pore creating material and the gross weight of noble metal and metal oxide containing precious metals
Ratio is aluminum oxide：Pore creating material：Gross weight=10~25 of noble metal and metal oxide containing precious metals：1~3：0.5~2, salpeter solution
Gross weight for material I gross weight 30~60%, it is further preferred that the gross weight of salpeter solution be material I gross weight
The 36~48% of amount.
In above-mentioned steps one, extruded moulding is carried out from the equipment of routine, in extruded moulding, according to actual need
The shape size of selection carrier is sought, preferred vector is cylinder.
In above-mentioned steps one, the pore creating material is removed by being calcined, then more ducts are formd in the carrier
So that load composition is uniformly distributed, and more load compositions can be supported, substantially increase and urged for quenching recovery gas alcohol
The catalytic activity of agent, at the same time, the quenching that is used for also advantageously finally obtained in raising reclaim gas catalyst for preparing alcohol
Stable type.
In above-mentioned steps one, in the preparation process of the carrier, extruded moulding is carried out from the equipment of routine,
In extruded moulding, the shape size of carrier is selected according to the actual requirements, and preferred vector is cylinder.In the preparation of the carrier
During, the pore creating material is removed by being calcined, then more ducts are formd in the carrier so that load composition is uniform
Distribution, and more load compositions can be supported, the catalytic activity for quenching recovery gas catalyst for preparing alcohol is substantially increased, with
This simultaneously, also advantageously in improve finally obtain be used for quenching recovery gas catalyst for preparing alcohol stable type.Furthermore it is preferred that
Atmosphere containing oxygen, such as be calcined in air atmosphere.
In above-mentioned steps one, preferably in the atmosphere containing oxygen, such as it is calcined in air atmosphere.
In above-mentioned steps one, it is calcined 1~6 hour preferably at 350~650 DEG C, it is further preferred that the temperature of roasting
For 400~550 DEG C, the time of roasting is preferably 2~5 hours, it is further preferred that the temperature of roasting is 500 DEG C, roasting
Time is 3~4 hours.
Step 2: four thio ammonium molybdate is dissolved in the water, maceration extract I is obtained, by chromic nitrate and potassium carbonate co-dissolve
Yu Shuizhong, maceration extract II is obtained, the carrier obtained in step 1 is put into after maceration extract I stands, then after being impregnated by maceration extract I
Carrier be dried, then dried carrier is put into maceration extract II and stood, is dried afterwards, after being impregnated
Carrier.
In above-mentioned steps two, the gross weight of chromic nitrate and potassium carbonate is 0.5~1 times of the gross weight of the carrier, is entered
Preferably, the gross weight of chromic nitrate and potassium carbonate is 0.5~0.8 times of the gross weight of the carrier to one step, the weight of chromic nitrate
For 0.5~2 times of the weight of four thio ammonium molybdate, the total amount of chromic nitrate is 0.5~1 times of the weight of four thio ammonium molybdate, carbon
The weight of sour potassium is 0.1~1 times of the weight of four thio ammonium molybdate, it is further preferred that the weight of potassium carbonate is tetrathio molybdenum
0.15~0.5 times of the weight of sour ammonium.
In above-mentioned steps two, four thio ammonium molybdate is commercially available, can also make acquisition by oneself.It is preferred that pass through following method
Synthesized：Ammonium paramolybdate and/or molybdenum trioxide are added in concentrated ammonia liquor and dissolved, then adds ammonium sulfide solution, is controlled
After temperature reacts 30min at 60~70 DEG C, reaction system is cooled to 0 DEG C of crystallization 60min, then reaction system entered successively
Row is filtered, deionized water is washed, absolute ethyl alcohol washs, is dried, and obtains rufous four thio ammonium molybdate crystal.Wherein, concentrated ammonia liquor
Mass percentage concentration be 50~80%, preferably the mass percent concentration of concentrated ammonia liquor be 60~70%, in particular it is preferred to dense ammonia
The mass percent concentration of water is 65%；The mass percent concentration of ammonium sulfide solution is 50~80%, preferably ammonium sulfide solution
Mass percent concentration be 60~75%, the mass percent concentration of ammonium sulfide solution is 65~70%.It should be noted that
When being dissolved from concentrated ammonia liquor to ammonium paramolybdate and molybdenum trioxide, the addition of concentrated ammonia liquor only need to be by dissolution of raw material.
The addition of ammonium sulfide causes the mole of the element sulphur in ammonium sulfide and rubbing for the molybdenum element in ammonium paramolybdate or molybdenum trioxide
The ratio between your amount is S：Mo=2.8~4.2:1.
In above-mentioned steps two, in the maceration extract I and in maceration extract II, the addition of water has no special limit
System, if will enable tetrathio molybdic acid, chromic nitrate and potassium carbonate be dissolved completely in water.
In above-mentioned steps two, the time that the carrier is stood in maceration extract I and in maceration extract II is excellent
Elect as 0.5~6 hour, it is further preferred that time of repose is 1~3 hour, it is further preferred that time of repose is 1~2
Hour.In addition, drying condition of the carrier respectively after maceration extract I and maceration extract II impregnate be both preferably 80~
Dried 1~5 hour at 140 DEG C, it is further preferred that the temperature dried is 90~120 DEG C, the dry time is 1~3 hour.
In addition, when being impregnated from maceration extract I and maceration extract II, as long as so that carrier is immersed in maceration extract, preferably soak
Stain liquid is identical with the volume of carrier.
Due in above-mentioned steps two, after drying, eliminating moisture of the absorption on carrier, being more beneficial for step 4
In roasting process so that it is final obtain it is more stable for quenching recovery gas catalyst for preparing alcohol.
It is used for above-mentioned in quenching recovery gas catalyst for preparing alcohol, chromic nitrate and potassium carbonate are adsorbed described by infusion process
On carrier, the infusion process, exactly the carrier is put into by both above-mentioned obtained solution, after standing, then nitric acid
Chromium and potassium carbonate adsorb on the carrier.Specifically, as described below：Four thio ammonium molybdate is dissolved in the water, soaked
Stain liquid I, by chromic nitrate and potassium carbonate co-dissolve in water, obtain maceration extract II；The carrier is put into maceration extract I to stand,
The carrier after being impregnated by maceration extract I is dried again, then carrier is placed again into maceration extract II, is dried again.
Step 3：Carrier after the dipping obtained in step 3 is calcined at 500~800 DEG C and under an inert atmosphere 2
~6 hours, obtain and reclaim gas catalyst for preparing alcohol for quenching.
In above-mentioned steps three, inert gas is the one or more in nitrogen, helium and argon gas, preferably nitrogen.
In above-mentioned steps three, it is preferable that the temperature of roasting is 500~700 DEG C, it is further preferred that the temperature of roasting
For 500~600 DEG C；Preferably, the time of roasting is 3~5 hours, it is further preferred that the time of roasting is 5 hours.
Due in the preparation method of gas catalyst for preparing alcohol is reclaimed provided by the present invention for quenching, eliminating pore creating material,
So that carrier provides more ducts for load composition, the content of the load composition on carrier is considerably increased, so as to improve
What is be finally prepared is used for the activity and stability of quenching recovery gas catalyst for preparing alcohol, in addition, provided by the present invention for
The preparation method of quenching recovery gas catalyst for preparing alcohol using the shaping of first carrier, after loaded by infusion process, and also use
The mode being calcined after load, avoid not uniform enough using load distribution caused by rear bearing body formed this kind of mode is first loaded
The problem of, and preparation method provided by the present invention is used, enable to load more preferable and being distributed on carrier evenly, from
And enable to give full play to its catalytic activity for quenching recovery gas catalyst for preparing alcohol.In addition, provided by the present invention for putting out
The preparation method of Jiao's recovery gas catalyst for preparing alcohol is simple, easy to operation, realizes industrialization, and low into production cost, is advantageous to advise greatly
The popularization of mould.
What preparation method provided by the present invention obtained is used for quenching recovery gas catalyst for preparing alcohol, and catalytic activity is higher, surely
Qualitative height, while use instead and had wide range of applications in quenching recovery gas catalyst for preparing alcohol, it can be used in by containing CO2And CH4Gas
Body, such as alcohol-based liquid is prepared into high-temperature flue gas caused by quenching, especially, low-carbon alcohols can be prepared into, wherein, institute
It is the alcohol that carbon number is 1~3 to state low-carbon alcohols, for example, methanol, ethanol, propyl alcohol etc..In addition, it is prepared into by high-temperature flue gas
Required reaction condition is gentle during alcohol-based liquid, and selective high, and the space-time yield of the alcohol-based liquid finally given is high, such as
In temperature in 240~360 DEG C and pressure under 4~8MPa reaction condition, the space-time yield of alcohol-based liquid can reach
More than 0.16g/hmLcat.
Embodiment
Embodiment
The present invention is further described below by way of instantiation.But these examples are only exemplary, not to this
The protection domain of invention forms any restrictions.Below by the present invention is described in detail, the features and advantages of the invention will
Become more apparent from, clearly with these explanations.
In following examples, comparative example and test example, used material, reagent and instrument are as without special theory
It is bright, it is that commercially acquisition conventional material or reagent therein can synthesize to obtain by conventional method.
In following embodiments 1~6, used four thio ammonium molybdate is prepared by following methods：
Ammonium paramolybdate and/or molybdenum trioxide are added in the concentrated ammonia liquor that mass percent concentration is 22~25% and are allowed to molten
Solution, the ammonium sulfide solution that mass percent concentration is 65% is then added, after control temperature reacts 30min at 60~70 DEG C,
Reaction system is cooled to 0 DEG C of crystallization 60min, then reaction system filtered with Buchner funnel successively, deionized water is washed, nothing
Water-ethanol washing, dry, obtain rufous four thio ammonium molybdate crystal.
It is above-mentioned prepare four thio ammonium molybdate crystal during, it is the amount of each material used, the species of molybdenum source, final
The amount of the four thio ammonium molybdate crystal arrived and the numbering of final product are as shown in Table 1 below.
Table 1
Embodiment 1：
(1) 14.42g alumina powders, 2.02g flocking powder and 0.51g gallium oxide powder are well mixed, obtained material I, will
The salpeter solution 7.12g that mass percent concentration is 10% is uniformly sprayed to obtain in material I, obtains material II, then to material
II extruded moulding, is put into Muffle furnace afterwards, and 4h is calcined in 500 DEG C and air atmosphere to remove flocking powder, obtains carrier；
(2) after being completely dissolved the foregoing four thio ammonium molybdate 1 prepared plus water, maceration extract I is obtained, by 23.77g nitric acid
Chromium and 6.20g potassium carbonate are added to a small amount of water and are completely dissolved jointly, obtain maceration extract II, are obtained in selection and step (1)
The isometric maceration extract I of carrier, resulting vehicle is put into after maceration extract I stands 2 hours, then 2h is dried under the conditions of 120 DEG C, so
The selection maceration extract II isometric with the carrier obtained in step (1) afterwards, maceration extract is put into by the carrier after being impregnated by maceration extract I
2 hours are stood in II, dries 2h, the carrier after being impregnated at 120 DEG C afterwards；
(3) roasting 5h is obtained the carrier after the dipping that will be obtained in step (2) at 600 DEG C and in a nitrogen atmosphere
43.63g's is used for quenching recovery gas catalyst for preparing alcohol, referred to as catalyst A.
Embodiment 2
(1) 13.80g alumina powders, 1.33g sesbania powders and 0.47g gallium oxide powder are well mixed, obtained material I, will
The salpeter solution 6.97g that mass percent concentration is 10% is uniformly sprayed to obtain in material I, obtains material II, then to material
II extruded moulding, is put into Muffle furnace afterwards, and 4h is calcined in 450 DEG C and air atmosphere to remove sesbania powder, obtains carrier；
(2) after being completely dissolved the foregoing four thio ammonium molybdate 2 prepared plus water, maceration extract I is obtained, by 22.62g nitric acid
Chromium and 6.31g potassium carbonate are added to a small amount of water and are completely dissolved jointly, obtain maceration extract II, are obtained in selection and step (1)
The isometric maceration extract I of carrier, resulting vehicle is put into after maceration extract I stands 2 hours, then 2.5h is dried under the conditions of 120 DEG C,
Then the selection maceration extract II isometric with the carrier obtained in step (1), dipping is put into by the carrier after being impregnated by maceration extract I
2 hours are stood in liquid II, dries 2.5h, the carrier after being impregnated at 120 DEG C afterwards；
(3) roasting 4h is obtained the carrier after the dipping that will be obtained in step (2) at 600 DEG C and in a nitrogen atmosphere
43.89g's is used for quenching recovery gas catalyst for preparing alcohol, referred to as catalyst B.
Embodiment 3
(1) 9.96g alumina powders, 1.63g flocking powder and 0.31g oxidation silver powder are well mixed, obtained material I will
The salpeter solution 4.93g that mass percent concentration is 10% is uniformly sprayed to obtain in material I, obtains material II, then to material
II extruded moulding, is put into Muffle furnace afterwards, and 4h is calcined in 450 DEG C and air atmosphere to remove flocking powder, obtains carrier；
(2) after being completely dissolved the foregoing four thio ammonium molybdate 3 prepared plus water, maceration extract I is obtained, by 25.92g nitric acid
Chromium and 7.15g potassium carbonate are added to a small amount of water and are completely dissolved jointly, obtain maceration extract II, are obtained in selection and step (1)
The isometric maceration extract I of carrier, resulting vehicle is put into after maceration extract I stands 2 hours, then 2h is dried under the conditions of 120 DEG C, so
The selection maceration extract II isometric with the carrier obtained in step (1) afterwards, maceration extract is put into by the carrier after being impregnated by maceration extract I
2 hours are stood in II, dries 2h, the carrier after being impregnated at 120 DEG C afterwards；
(3) roasting 5h is obtained the carrier after the dipping that will be obtained in step (2) at 600 DEG C and in a nitrogen atmosphere
44.61g's is used for quenching recovery gas catalyst for preparing alcohol, referred to as catalyst C.
Embodiment 4
(1) 10.08g alumina powders, 0.79g flocking powder and 0.26g bronzes are well mixed, obtained material I, by quality
The salpeter solution 5.61g that percent concentration is 10% is uniformly sprayed to obtain in material I, obtains material II, then material II is squeezed
Bar is molded, and is put into afterwards in Muffle furnace, and 3h is calcined in 500 DEG C and air atmosphere to remove flocking powder, obtains carrier；
(2) after being completely dissolved the foregoing four thio ammonium molybdate 4 prepared plus water, maceration extract I is obtained, by 22.41g nitric acid
Chromium and 5.86g potassium carbonate are added to a small amount of water and are completely dissolved jointly, obtain maceration extract II, are obtained in selection and step (1)
The isometric maceration extract I of carrier, resulting vehicle is put into after maceration extract I stands 2 hours, then 2.5h is dried under the conditions of 120 DEG C,
Then the selection maceration extract II isometric with the carrier obtained in step (1), dipping is put into by the carrier after being impregnated by maceration extract I
2 hours are stood in liquid II, dries 2.5h, the carrier after being impregnated at 120 DEG C afterwards；
(3) roasting 5h is obtained the carrier after the dipping that will be obtained in step (2) at 550 DEG C and under an argon atmosphere
44.65g's is used for quenching recovery gas catalyst for preparing alcohol, referred to as catalyst D.
Embodiment 5
(1) 15.33g alumina powders, 1.91g sesbania powders and 0.59g gallium oxide powder are well mixed, material I are obtained, by matter
The salpeter solution 7.85g that amount percent concentration is 10% is uniformly sprayed in obtained material I, obtains material II, then to material
II extruded moulding, is put into Muffle furnace afterwards, and 4h is calcined in 500 DEG C and air atmosphere to remove sesbania powder, obtains carrier；
(2) after being completely dissolved the foregoing four thio ammonium molybdate 5 prepared plus water, maceration extract I is obtained, by 23.26g nitric acid
Chromium and 6.54g potassium carbonate are added to a small amount of water and are completely dissolved jointly, obtain maceration extract II, are obtained in selection and step (1)
The isometric maceration extract I of carrier, resulting vehicle is put into after maceration extract I stands 2 hours, then 2h is dried under the conditions of 120 DEG C, so
The selection maceration extract II isometric with the carrier obtained in step (1) afterwards, maceration extract is put into by the carrier after being impregnated by maceration extract I
2 hours are stood in II, dries 2h, the carrier after being impregnated at 120 DEG C afterwards；
(3) roasting 5h is obtained the carrier after the dipping that will be obtained in step (2) at 600 DEG C and in a nitrogen atmosphere
43.63g's is used for quenching recovery gas catalyst for preparing alcohol, referred to as catalyst E.
Embodiment 6
(1) 17.79g alumina powders, 1.32g flocking powder and 0.30g gallium oxide powder are well mixed, material I are obtained, by matter
The salpeter solution 9.34g that amount percent concentration is 10% is uniformly sprayed in obtained material I, obtains material II, then to material
II extruded moulding, is put into Muffle furnace afterwards, and 4h is calcined in 500 DEG C and air atmosphere to remove flocking powder, obtains carrier；
(2) after being completely dissolved the foregoing four thio ammonium molybdate 6 prepared plus water, maceration extract I is obtained, by 37.24g nitric acid
Chromium and 12.21g potassium carbonate are added to a small amount of water and are completely dissolved jointly, obtain maceration extract II, are obtained in selection and step (1)
The isometric maceration extract I of carrier, resulting vehicle is put into after maceration extract I stands 2 hours, then 2h is dried under the conditions of 120 DEG C, so
The selection maceration extract II isometric with the carrier obtained in step (1) afterwards, maceration extract is put into by the carrier after being impregnated by maceration extract I
2 hours are stood in II, dries 2h, the carrier after being impregnated at 120 DEG C afterwards；
(3) carrier after the dipping that will be obtained in step (2) is calcined 5h at 600 DEG C and under helium atmosphere and obtained
44.62g's is used for quenching recovery gas catalyst for preparing alcohol, referred to as catalyst F.
Test example
Catalyst A~the F obtained in embodiment is tested by the following method：
Using micro fixed-bed reactor by caused high-temperature flue gas during quenching, and what is obtained in embodiment urges
Alcohol-based liquid is prepared under the catalytic action of agent, wherein, the key component of high-temperature flue gas and corresponding volume fraction are as follows：
CO：28.81%th, H2：44.12%th, CO2：18.05%th, CH4：9.02%, reaction condition is as follows：Pressure is 7.5MPa, and temperature is
350 DEG C, the air speed of high-temperature flue gas is 5000h-1, the amount of fill of catalyst is 20mL, and the catalyst obtained in each embodiment is urged
Test result obtained by change high-temperature flue gas is as shown in table 2 below.
Table 2
Note：In above-mentioned table 2, the percentage representation quality percentage in alcohol distribution.
From above-mentioned table 2, it can learn：It can be incited somebody to action for quenching recovery gas catalyst for preparing alcohol by what the present invention was prepared
High-temperature flue gas during quenching is prepared into alcohol-based liquid, and obtained alcohol-based liquid space-time yield is higher, at the same time also has
Higher reaction selectivity, further, it is also possible to learn, it can individually obtain mass percent higher methanol and carbon number
Alcohol-based liquid more than or equal to 2.
The announcement of book according to the above description, those skilled in the art in the invention can also be carried out to above-mentioned embodiment
Appropriate change and modification.Therefore, the invention is not limited in embodiment disclosed and described above, to the present invention's
Some modifications and changes should also be as falling into the scope of the claims of the present invention.
Claims (10)
1. a kind of preparation method for quenching recovery gas catalyst for preparing alcohol, it is characterised in that comprise the following steps：
(1) after, mixing aluminum oxide, pore creating material and noble metal and/or metal oxide containing precious metals, material I is obtained, nitric acid is molten
Liquid is added in the material I, obtains material II, and then the material II is carried out to extruded moulding, roasting successively, carried
Body；
(2), four thio ammonium molybdate is dissolved in the water, obtains maceration extract I, by chromic nitrate and potassium carbonate co-dissolve in water,
Maceration extract II is obtained, the carrier obtained in step (1) is put into after maceration extract I stands, then by the carrier after being impregnated by maceration extract I
It is dried, then dried carrier is put into maceration extract II and stood, is dried afterwards, the carrier after being impregnated；
(3), roasting 2~6 is small at 500~800 DEG C and under an inert atmosphere for the carrier after the dipping that will be obtained in step (2)
When, obtain and reclaim gas catalyst for preparing alcohol for quenching.
2. the preparation method according to claim 1 for quenching recovery gas catalyst for preparing alcohol, it is characterised in that described to make
One or more of the hole agent in sesbania powder and flocking powder.
3. the preparation method according to claim 1 for quenching recovery gas catalyst for preparing alcohol, it is characterised in that described expensive
One or more of the metal in gold, silver, gallium, ruthenium, rhodium, palladium, osmium, iridium and platinum.
4. the preparation method according to claim 1 for quenching recovery gas catalyst for preparing alcohol, it is characterised in that described expensive
One or more of the metal oxide in gallium oxide and silver oxide.
5. the preparation method according to claim 1 for quenching recovery gas catalyst for preparing alcohol, it is characterised in that described
In step (1), the ratio of the weight of aluminum oxide, the weight of pore creating material and the gross weight of noble metal and metal oxide containing precious metals is oxygen
Change aluminium：Pore creating material：Gross weight=10~45 of noble metal and metal oxide containing precious metals：0.5~5：0.3~2,
The gross weight of salpeter solution is the 30~60% of the gross weight of the material I.
6. the preparation method according to claim 1 for quenching recovery gas catalyst for preparing alcohol, it is characterised in that described
In step (2), the weight of chromic nitrate is 0.5~2 times of the weight of four thio ammonium molybdate, and the weight of potassium carbonate is tetrathio molybdic acid
0.1~1 times of the weight of ammonium,
The gross weight of chromic nitrate and potassium carbonate is 0.5~1 times of the weight of the carrier.
7. the preparation method according to claim 1 for quenching recovery gas catalyst for preparing alcohol, it is characterised in that described
In step (1), the material II is calcined 1~6 hour at 350~650 DEG C and in the atmosphere containing oxygen and made with removing
Hole agent.
8. the preparation method according to claim 1 for quenching recovery gas catalyst for preparing alcohol, it is characterised in that described
In step (2),
The time that the carrier is stood in maceration extract I and in maceration extract II is 0.5~6 hour.
9. the preparation method according to claim 1 for quenching recovery gas catalyst for preparing alcohol, it is characterised in that described
In step (2), after maceration extract I and maceration extract II impregnate, it is small to dry 1~5 respectively at 80~140 DEG C for the carrier
When.
10. the preparation method according to claim 1 for quenching recovery gas catalyst for preparing alcohol, it is characterised in that in institute
State in step (3), the inert gas is the one or more in nitrogen, helium and argon gas.
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