CN1289638A - Process for preparing Cu-contained catalyst - Google Patents
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Abstract
A process for preparing Cu-contained catalyst includes such steps as depositing the Cu-contained ion solution with precipitant, mixing alumina with the deposit (or co-depositing with said Cu-contained ion solution) to obtain base catalyst, and loading alkali-metal elements to catalyst by immersing or spraying method. Obtained catalyst features high mechanical strength, high antiwear nature, high activity, and selectivity, less by-reaction, and low carbon deposit speed.
Description
The preparation method of the relevant a kind of Cu-contained catalyst of this patent.
Cu-contained catalyst is used for hydrogenation and dehydrogenation reaction has had for a long time, though its activity is strong not as catalyst such as nickel, using does not have it extensive yet, is obtaining application widely aspect the dehydrogenation of the hydrogenation of carbonyls and alcohol.In order to increase activity of such catalysts, the copper content in the catalyst is quite high, and promptly the cupric oxide content in the catalyst is very high, and like this, the processability of catalyst is poor, and the mechanical strength after the moulding is low, some in addition can only use with powder type.And low activity of such catalysts and the selectivity of copper content is very low, and show short service life.Though can adopt to add helps catalyst component such as zinc, chromium, magnesium, calcium to wait the content that reduces copper and disperse the copper crystallite, but the processability of these metal oxides is still relatively poor, be added with the general compression molding of copper catalyst of these oxides, the mechanical strength after the moulding is low.Mechanical strength is too poor, and except easy fragmentation in transporting and loading, efflorescence induces reaction the conversion ratio reduction until the catalyst termination in service life gradually in the running use, and catalyst is shorter service life.
Chinese patent CN1056067 has introduced a kind of cyclohexanol dehydrogenation catalyst, contains CuO, ZnO, MgO, CaO and micro-Na
2O.During preparation, behind above ion mixed solution alkaline chemical precipitation, after grinding, the roasting, do not add bonding agent, moisture regain back compression molding, like this, because above oxide powder processability is poor, belong to catalyst exoskeletal, no bonding composition, the mechanical strength of moulding rear catalyst is low, and easily efflorescence is its shortcoming.
BP 1,500,884 introduce, and with the silicic acid powder of extreme efflorescence, add in the precipitation of hydroxide of Cu, Cr, Mg, after mixing, obtain finished catalyst behind the compression molding.The crushing force of the catalyst granules that compressing tablet makes is 5-10Kg, and the crushing force after the reduction is 2-5Kg.This catalyst is used for the dehydrogenation of sec-butyl alcohol, and under 260 ℃, condition of normal pressure, conversion ratio is 85%, and the MEK selectivity is 95%.The selectivity of this catalyst dehydrogenation slightly increases, but because the adhesive property of powder silicic acid is still strong inadequately, the mechanical strength of catalyst is still very low.
If adopt the material of inertia to prepare catalyst, as the α-Al of macropore as carrier
2O
3, because its absorption property is very poor,, can only support very a spot of copper if support the copper metal, the reaction temperature of requirement is very high.As United States Patent (USP) 4453015, Cu, Zn, Cr are dipped in the α-Al of macropore
2O
3Go up as mellow wine dehydrogenating, be used for sec-butyl alcohol dehydrogenizing, 380 ℃ of reaction temperatures are at sec-butyl alcohol charging air speed 6h
-1Under the condition, sec-butyl alcohol conversion ratio 93.4%, the MEK selectivity is 93.6%.But because reaction temperature is too high, catalyst carbon deposition is too fast.
And use immersion process for preparing catalyst, then need to have the carrier of special specific area and definite shape and intensity, as the aluminium oxide of special type, silica, diatomite, float stone, molecular sieve etc., produce or purchase such carrier concerning catalyst manufacturer, can increase the cost of catalyst prod, compare with coprecipitation, it is high that the cost of the catalyst that infusion process makes is wanted.
The purpose of this patent is to provide a kind of preparation method of Cu-contained catalyst, improves catalyst activity and selectivity, and improves simultaneously its mechanical strength and service life.
Technical scheme of the present invention is as follows:
A kind of scheme is:
1, with after copper ions solution, the co-precipitation of aluminium ion solution adding precipitating reagent, be dried to little wet then;
2, moulding, roasting obtains base catalyst;
3, go on foot the base catalyst dipping of gained or spray alkali metal salt soln carrying alkali metal oxide to (2);
4, roasting obtains final catalyst.
Another kind of scheme is:
1, with after the co-precipitation of copper ions solution adding precipitating reagent, dry then, add aluminium hydroxide and make binding agent, and make it to mix fully; (can spray a spot of rare nitric acid) to little wet
2, moulding, roasting obtains base catalyst;
3, go on foot gained base catalyst dipping or spray alkali metal salt soln carrying alkali metal oxide to (2);
4, roasting obtains final catalyst
More than the copper ions solution described in two kinds of schemes, comprise copper ion, according to requirement, can comprise cocatalyst component simultaneously to catalytic component, also can not comprise catalytic component.Helping catalyst component is in zinc, magnesium, chromium, calcium, manganese, the iron one or more.
Described zinc, magnesium, chromium, calcium, manganese, iron, copper, aluminium ion solution can be one or more of nitrate, chlorate, sulfate mixed solution.
Described precipitating reagent can be an alkaline precipitating agent, also can be the organic acid precipitating reagent; Alkaline precipitating agent wherein can alkali-metal hydroxide, the solution of carbonated or carbonic acid hydride, as: sodium carbonate, NaOH, potash, potassium hydroxide etc.; Also can be the organic acid precipitating reagent, as ethanedioic acid, malonic acid, succinic acid etc.
Described forming method can be methods such as compressing tablet, extrusion or a ball, and the method for compressing tablet is good slightly.If adopt the method for compressing tablet, the graphite powder that generally can add 2%～5% (m) is made lubricant.
Described alkali metal oxide is one or more in lithium, sodium, potassium, rubidium, the caesium oxide.Described alkali metal salt soln is one or more in alkali-metal nitrate, chlorate, sulfate, the bicarbonate solution.
Below further the present invention is described in detail.
1, the preparation of base catalyst:
In 60～95 ℃ of temperature and pH value under the condition 6～9, add the aqueous slkali co-precipitation to the copper ions mixed solution, after the drying precipitate, with aluminium-hydroxide powder and above sediment powder evenly after, spray rare salpeter solution to little wet, add an amount of graphite, compression molding makes base catalyst behind the drying and roasting.
Or:
Aluminium ion solution is mixed with copper ions solution, add aqueous slkali (precipitating reagent can not be acid) co-precipitation under the condition 6～9 in 60～95 ℃ of temperature and pH value, drying precipitate adds an amount of graphite to little wetting, compression molding, dry, roasting obtains base catalyst.
The concentration of solion and precipitating reagent is between 0.5～3.0M, and is better with the low concentration of 0.5～2M.Preferably control co-precipitation temperature and the pH value is constant.The process of co-precipitation can take solion and precipitant solution to add method in the container, promptly so-called cocurrent adding material method simultaneously.
Described sintering temperature is 300～400 ℃.
2. the appendix of alkali metal oxide
With above two kinds of base catalysts that method makes, with concentration is that the alkali-metal salting liquid of 0.5～3.0M floods, dipping can adopt solution to soak, add means such as hot reflux, evaporation, perhaps with means such as certain concentration solution spray, the matrix behind the dipping obtains final catalyst by drying and roasting.
The concentration of alkali metal maceration extract is 0.5～4.0M; Dipping temperature is 0～100 ℃, preferably 60～100 ℃; The roasting under 300～400 ℃ condition of dipping rear catalyst.
Like this, catalyst of the present invention is made up of cupric oxide, aluminium oxide, alkali metal oxide when not going back ortho states, contains or do not contain the oxide that helps catalyst component zinc, chromium, magnesium, calcium, manganese, iron.In this catalyst, the content of cupric oxide is between 10%～90m%, and optimum content is between 30%～60m%; The alkali metal oxide of appendix can be one or more in lithium, sodium, potassium, rubidium, the caesium oxide, and its content is between 0.1%～4.0m%, and is best between 0.3%～3.0m%; The content of aluminium oxide is between 5%～40m%, and the best is 10%～30m%; Can contain one or more the oxide in zinc, chromium, magnesium, calcium, manganese, the iron, content is 0%～50m%, and the best is 10%～45%.
By the catalyst that above method makes, carry out the mechanical strength test, be 20.0～28.0MPa before the average crushing strength reduction of catalyst granules; After the reduction 14.3～20.0MPa.
This catalyst at first should reduce before use, and reduction is generally after catalyst is packed reactor into, between 150～200 ℃, reduce with nitrogen and hydrogen mixture, hydrogen concentration raises gradually during reduction, it is constant to import and export hydrogen concentration to reactor, when reactor does not have water generates till.When being used for alcohol dehydrogenase, also can when 150～200 ℃ of left and right sides, directly advancing raw polyol catalyst is reduced.
Catalyst of the present invention is applicable to hydrogenation reaction of the reaction of fabricated by dehydrogenating alcohol aldehyde, ketone of gas-solid phase and aldehyde, ketone etc.
Preparation of catalysts method of the present invention has following advantage: one, catalyst is main active constituent with copper, adds oxides such as zinc, magnesium, chromium, in the preparation, after co-precipitation, obtain base catalyst, the mechanical strength height of the catalyst of acquisition for the bonding agent moulding with the aluminium oxide; Two, the base catalyst dipping that makes more than the general is gone up alkali metal oxide, has reduced the side reaction activity of catalyst, has improved its selectivity and service life; Three, in the Preparation of catalysts process, coprecipitation is adopted in the preparation of base catalyst, and last alkali metal gets on by easy dipping appendix of a step, and it is simple to have preparation process, and the catalyst cost is low.
Embodiment
Base catalyst preparation example 1
Preparation one contains 3 liters of deion aqueous solutions of 338g copper nitrate, 254g zinc nitrate and 220g aluminum nitrate, as mixing salt solution.Again 498 sodium carbonate are dissolved in 3 liters of deionized waters as precipitating reagent.
Above two kinds of solution are heated to 85 ℃ in hot bath, and will add low amounts of water in the large beaker, in same hot bath, be heated to 85 ℃, under quick stirring, above mixed solution and precipitating reagent evenly also flow and add in the beaker, keep in about 15 minutes, adding between 85 ℃ of bath temperatures and the suspension pH value 7.0～8.0, after splash into small amounts of sodium hydroxide solution again and regulate pH value to 9.5.Sediment is after aging half an hour, filter and with after the deionized water washes clean, be dried to little wet, adding the 25g graphite powder mixes, be pressed into 4 * 4 cylinder with tablet press machine, 380 ℃ of roastings make base catalyst A305g, consist of cupric oxide 46%, zinc oxide 35.5%, aluminium oxide 18.5%.
Base catalyst preparation example 2
Preparation one contains 4 liters of deion aqueous solutions of 375g copper nitrate, 293g chromic nitrate and 13.6g magnesium nitrate, as mixing salt solution.Again 366g NaOH is dissolved in 4 liters of deionized waters as precipitating reagent.
Above two kinds of solution are heated to 70 ℃ in hot bath, and will add low amounts of water in the large beaker, in same hot bath, be heated to 70 ℃, under quick stirring, above mixed solution and precipitating reagent evenly also flow and add in the beaker, keep in about 15 minutes, adding between 70 ℃ of bath temperatures and the suspension pH value 7.5～9.0.Sediment is after aging half an hour, filter and with after the deionized water washes clean, fully dry, mix with the 123g aluminium hydrate powder after grinding to form fine powder, an amount of rare nitric acid adds a small amount of graphite powder to evenly little wet in the spraying, mixes the back compression molding, make base catalyst B402g after 380 ℃ of roastings, consist of cupric oxide 37.8%, chromium oxide 30.0%, magnesia 12.1%, aluminium oxide 20.0%.
Base catalyst preparation example 3
Preparation one contains 3 liters of deion aqueous solutions of 269g copper chloride, 84.6g manganese chloride and 32.2g ferric trichloride, as mixing salt solution.Again 238 sodium carbonate are dissolved in 3 liters of deionized waters as precipitating reagent.
Above two kinds of solution are heated to 85 ℃ in hot bath, and will add low amounts of water in the large beaker, in same hot bath, be heated to 85 ℃, under quick stirring, above mixed solution and precipitating reagent evenly also flow and add in the beaker, keep in about 15 minutes, adding between 85 ℃ of bath temperatures and the suspension pH value 7.0～8.0, after splash into small amounts of sodium hydroxide solution again and regulate pH value to 9.5.Sediment is after aging half an hour, filter and with after the deionized water washes clean, fully dry, mix with the 116g aluminium hydrate powder after grinding to form fine powder, an amount of rare nitric acid adds a small amount of graphite powder to evenly little wet in the spraying, mixes the back compression molding, make base catalyst C303g after 380 ℃ of roastings, consist of cupric oxide 50.1%, manganese oxide 14.9%, ferric oxide 10.0%, aluminium oxide 25.0%.
Base catalyst preparation example 4
2 liters of deion aqueous solutions that prepare a sulfur acid copper 478.5g.Again 318g sodium carbonate is dissolved in 2 liters of deionized waters as precipitating reagent.
Above two kinds of solution are heated to 85 ℃ in hot bath, and will add low amounts of water in the large beaker, in same hot bath, be heated to 85 ℃, under quick stirring, above mixed solution and precipitating reagent evenly also flow and add in the beaker, keep in about 10 minutes, adding between 85 ℃ of bath temperatures and the suspension pH value 7.0～8.0, after splash into small amounts of sodium hydroxide solution again and regulate pH value to 9.5.Sediment is after aging half an hour, filter and use the deionized water washes clean, fully dry, mix with the 231g aluminium hydrate powder after grinding to form fine powder, an amount of rare nitric acid mixes and pinches fully to evenly little wet in the spraying, be extruded into strip with banded extruder, oven dry makes base catalyst D378g after 380 ℃ of roastings, consists of cupric oxide 60%, aluminium oxide 40%.
Finished catalyst preparation example 1
2 liters of the potassium nitrate solutions of preparation 1.5mol/L are standby.
Respectively get the above base catalyst Al50g that makes, put into a flask, flask is furnished with the water condensation return channel, the potassium nitrate solution 300ml that adds 1.5mol/L, added hot reflux 3 hours, obtain final catalyst A after back drying, 360 ℃ of roastings, consist of cupric oxide 45.4%, zinc oxide 35.1%, aluminium oxide 18.3%, potassium oxide 1.2%.The average crushing strength of catalyst granules is 22.0MPa; The reduction back is 16.0MPa.
Finished catalyst preparation example 2
Getting 6.5g potassium nitrate is dissolved in the 30ml deionized water standby.
Get the base catalyst A200g of above preparation, in 120 ℃ of dryings 8 hours, spraying in the pot of the rotation of packing into immediately after the cooling sprayed into above KNO
3Solution, after the oven dry, 360 ℃ of roastings obtain finished catalyst B, and catalyst consists of: cupric oxide 37.4%, chromium oxide 29.6%, magnesia 11.9%, aluminium oxide 19.7%, potassium oxide 1.4%.The average crushing strength of catalyst granules is 26.0MPa; The reduction back is 20.0MPa.
Finished catalyst preparation example 3
Getting 5.5g sodium carbonate is dissolved in the 30ml deionized water standby.
Get the base catalyst C200g of above preparation, in 120 ℃ of dryings 8 hours, pack into immediately after the cooling one the rotation spray in the pot, spray into above sodium carbonate liquor, after the oven dry, 390 ℃ of roastings obtain finished catalyst C, catalyst consists of: cupric oxide 49.4%, manganese oxide 14.7%, di-iron trioxide 9.8%, aluminium oxide 24.6%, sodium oxide molybdena 1.5%.The average crushing strength of catalyst granules is 20.0MPa; The reduction back is 16.0MPa.
Finished catalyst preparation example 4
Getting 14g potassium nitrate is dissolved in the 30ml deionized water standby.
Get the base catalyst A200g of above preparation, in 120 ℃ of dryings 8 hours, spraying in the pot of the rotation of packing into immediately after the cooling sprayed into above KNO
3Solution, after the oven dry, 360 ℃ of roastings obtain finished catalyst B, and catalyst consists of: cupric oxide 58.3%, aluminium oxide 38.9%, potassium oxide 2.8%.The average crushing strength of catalyst granules is 23.0MPa; The reduction back is 17.0MPa.
Finished catalyst preparation example 5
The cesium nitrate solution 300ml of preparation 2M.Get the above base catalyst Al50g that makes, put into a flask, flask is furnished with the water condensation return channel, all add above cesium nitrate solution, added hot reflux 3 hours, obtain final catalyst E after back drying, 380 ℃ of roastings, consist of cupric oxide 45.3%, zinc oxide 35.0%, aluminium oxide 18.2%, cesium oxide 1.5%.The average crushing strength of catalyst granules is 20.0MPa; The reduction back is 14.0MPa.
Preparation of Catalyst comparative example 1
To make mixing salt solution in 340g copper nitrate and 3 liters of deionized waters of 255g zinc nitrate adding.To make precipitant solution in 3 liters of deionized waters of 330g sodium carbonate liquor 330g adding.
Above two kinds of solution are heated 85 ℃ of systems in hot bath, and will add low amounts of water in the large beaker, in same hot bath, be heated to 85 ℃, under quick stirring, above mixed solution and precipitating reagent evenly also flow and add in the beaker, keep in about 10 minutes, adding between 85 ℃ of bath temperatures and the suspension pH value 7.0～7.5, after splash into small amounts of sodium hydroxide solution again and regulate pH value to 9.5.Sediment is after aging half an hour, filters and with after the deionized water washes clean, and is dry complete, after the roasting, adds a small amount of graphite powder and grinds to form fine powder, sprays into compression molding behind a little moisture and be 4 * 4 cylinder.The average crushing strength of moulding rear catalyst particle is 4.0MPa, and after the reduction, crushing strength is 2.5MPa.
Application examples 1-5
With above each 40ml of the catalyst A-E that makes, press certain particle size, be loaded on respectively in the tubular reactor of internal diameter 15mm, in the time of 150-200 ℃ with after the nitrogen and hydrogen mixture reduction, enter sec-butyl alcohol by 160ml per hour, under 260 ℃ of reaction temperatures, normal pressure, sec-butyl alcohol dehydrogenizing prepares MEK, during reaction result is listed in the table below.
Be defined as follows notion:
The conversion ratio of sec-butyl alcohol=(the total sec-butyl alcohol amount of sec-butyl alcohol amount/charging that conversion is fallen) * 100% generates selectivity=(the sec-butyl alcohol amount that the sec-butyl alcohol amount/conversion of generation MEK is fallen) * 100% of MEK
| Instance number | The catalyst numbering | The conversion ratio of sec-butyl alcohol, % | Generate the selectivity of MEK, % |
| ????1 ????2 ????3 ????4 ????5 | ????A ????B ????C ????D ????E | ????88．3 ????89．0 ????93．2 ????94．2 ????87．4 | ????98．0 ????97．8 ????93．5 ????92．5 ????97．8 |
Utilize catalyst A, at 260 ℃, volume space velocity LSHV=4.0h during charging sec-butyl alcohol liquid
-1, under the normal pressure, the result of example 1 is continuous in the table in the maintenance turned round 2000 hours, and the conversion ratio of sec-butyl alcohol is not seen reduction.
Use comparative example 1
With the above base catalyst A that makes, be directly used in reaction.This catalyst is used for the dehydrogenation of sec-butyl alcohol by embodiment 1 identical condition, and the conversion ratio of sec-butyl alcohol is 91.2%, and the selectivity of the MEK that reaction generates has only about 86%.Be reflected at carry out 400 hours after, the conversion ratio of sec-butyl alcohol begins to descend, and illustrates that the carbon distribution speed of catalyst is very fast.
Application examples 6
With the catalyst A 80ml that above method makes, be loaded in the tubular reactor of internal diameter 15mm, 150-200 ℃ with after the nitrogen oxygen atmosphere reduction, reactor is warming up to 260 ℃, enters the alcohol vapour that is preheated to reaction temperature, the liquid volume air speed of feed ethanol is 1.0h
-1, after the dehydrogenation reaction, ethanol conversion is 55%, and the selectivity that generates acetaldehyde is 93%.
Application examples 7
Make catalyst A 40ml more than inciting somebody to action, be loaded in the tubular reactor of internal diameter 15mm, 150-200 ℃ with after the nitrogen oxygen atmosphere reduction, reactor is warming up to 260 ℃, enter the steam of the cyclohexanol that is preheated to reaction temperature, the liquid volume air speed of charging cyclohexanol is 2.0h
-1, after the dehydrogenation reaction, the conversion ratio of cyclohexanol can reach more than 80%, and the selectivity that generates cyclohexanone is 99.5%.
Application examples 8
With the above catalyst A 80ml that makes, in the tubular reactor of the internal diameter 15mm that packs into, 150-200 ℃ with after the nitrogen oxygen atmosphere reduction, reactor constant temperature enters the mixture of hutanal steam and hydrogen at 150 ℃, the liquid volume air speed of charging hutanal is 1.0h
-1, hydrogen is 1000: 1 in the volume ratio of feed liquid butyraldehyde, and reactor pressure is 2.0MPa, carries out the hydrogenation reaction of hutanal, and after the reaction, the conversion ratio of hutanal can reach more than 99.8%, and the selectivity that generates n-butanol is 99.9%.
Application examples 9
Make catalyst A 80ml more than inciting somebody to action, pack in the tubular reactor of internal diameter 15mm, 150-200 ℃ with the nitrogen oxygen atmosphere reduction after, reactor constant temperature is at 150 ℃, enter the mixture of 2-ethyl hexanal steam and hydrogen, the liquid volume air speed of charging 2-ethyl hexanal is 1.0h
-1, hydrogen is 1000: 1 in the volume ratio of feed liquid butyraldehyde, and reactor pressure is 2.0MPa, carries out the hydrogenation reaction of 2-ethyl hexanal, and after the reaction, the conversion ratio of 2-ethyl hexanal can reach more than 99.8%, and the selectivity that generates 2-Ethylhexyl Alcohol is 99.9%.
Claims (29)
1, a kind of preparation method of Cu-contained catalyst comprises: after (1) adds the precipitating reagent co-precipitation with copper ions solution, aluminium ion solution, dry then; (2) moulding, roasting obtains base catalyst; (3) to the base catalyst of (2) gained dipping or spray alkali metal soln carrying alkali metal oxide; (4) roasting obtains final catalyst.
2,, it is characterized in that described copper ions solution comprises copper ion and the salting liquid that helps catalyst component according to the preparation method of the described Cu-contained catalyst of claim 1.
3,, it is characterized in that described co-precipitation condition is: 60～95 ℃ of precipitation temperatures according to the preparation method of the described Cu-contained catalyst of claim 1; PH value 6～9; Concentration 0.5～the 3.0M of solion and precipitant solution.
4,, it is characterized in that described precipitating reagent is alkaline precipitating agent or organic acid precipitating reagent according to the preparation method of the described Cu-contained catalyst of claim 1.
5,, it is characterized in that described forming method is that compressing tablet is shaped according to the preparation method of the described Cu-contained catalyst of claim 1.
6,, it is characterized in that described alkali metal oxide is one or more of lithium, sodium, potassium, rubidium, caesium oxide according to the preparation method of the described Cu-contained catalyst of claim 1.
7,, it is characterized in that the temperature of described roasting acquisition base catalyst is 300～400 ℃ according to the preparation method of the described Cu-contained catalyst of claim 1.
8,, it is characterized in that the temperature that described roasting obtains final catalyst is 300～400 ℃ according to the preparation method of the described Cu-contained catalyst of claim 1.
9,, it is characterized in that described alkali metal salt soln is one or more in alkali-metal nitrate, chlorate, sulfate, carbonate, the bicarbonate solution according to the preparation method of the described Cu-contained catalyst of claim 1.
10, according to the preparation method of the described Cu-contained catalyst of claim 1, it is characterized in that described dipping or the condition that sprays are: 0～100 ℃ of dipping temperature, the concentration of alkali metal maceration extract is between 0.5～4.0M
11,, it is characterized in that the described catalyst component that helps is in zinc, magnesium, calcium, manganese, chromium, the iron one or more according to the preparation method of the described Cu-contained catalyst of claim 2.
12,, it is characterized in that described copper and the solion that helps catalyst component are one or more in nitrate, chlorate, the sulfate according to the preparation method of the described Cu-contained catalyst of claim 2.
13, a kind of preparation method of Cu-contained catalyst comprises:
(1) with after the co-precipitation of copper ions solution adding precipitating reagent, dry then, add aluminium hydroxide and make binding agent, and make it to mix fully;
(2) moulding, roasting obtains base catalyst;
(3) go on foot gained base catalyst dipping or spray alkali metal soln carrying alkali metal oxide to (2);
(4) roasting obtains final catalyst
14,, it is characterized in that described copper ions solution comprises copper ion and the salting liquid that helps catalyst component according to the preparation method of the described Cu-contained catalyst of claim 13.
15,, it is characterized in that described co-precipitation condition is: 60～95 ℃ of precipitation temperatures according to the preparation method of the described Cu-contained catalyst of claim 13; PH value 6～9; Concentration 0.5～the 3.0M of solion and precipitant solution.
16,, it is characterized in that described precipitating reagent is an alkaline precipitating agent according to the preparation method of the described Cu-contained catalyst of claim 13.
17,, it is characterized in that described precipitating reagent is the organic acid precipitating reagent according to the preparation method of the described Cu-contained catalyst of claim 13.
18,, it is characterized in that described forming method is that compressing tablet is shaped according to the preparation method of the described Cu-contained catalyst of claim 13.
19,, it is characterized in that described alkali metal oxide is one or more of lithium, sodium, potassium, rubidium, caesium oxide according to the preparation method of the described Cu-contained catalyst of claim 13.
20,, it is characterized in that the temperature of described roasting acquisition base catalyst is 300～400 ℃ according to the preparation method of the described Cu-contained catalyst of claim 13.
21,, it is characterized in that the temperature that described roasting obtains final catalyst is 300～400 ℃ according to the preparation method of the described Cu-contained catalyst of claim 13.
22,, it is characterized in that described alkali metal salt soln is one or more in alkali-metal nitrate, chlorate, sulfate, carbonate, the bicarbonate solution according to the preparation method of the described Cu-contained catalyst of claim 13.
23, according to the preparation method of the described Cu-contained catalyst of claim 13, it is characterized in that described dipping or the condition that sprays are: 0～100 ℃ of dipping temperature, the concentration of alkali metal maceration extract is between 0.5～4.0M.
24,, it is characterized in that the described catalyst component that helps is in zinc, magnesium, calcium, manganese, chromium, the iron one or more according to the preparation method of the described Cu-contained catalyst of claim 14.
25,, it is characterized in that described copper and the solion that helps catalyst component are one or more in nitrate, chlorate, the sulfate according to the preparation method of the described Cu-contained catalyst of claim 14.
26, a kind of Cu-contained catalyst, percentage by weight with catalyst is a benchmark, consist of cupric oxide 10%～90%, the oxide that helps catalyst component is 0%～50%, aluminium oxide is 5%～40%, it is characterized in that catalyst also comprises 0.1%～4.0% alkali metal oxide, is 20.0～28.MPa before the average crushing strength reduction of catalyst granules, is 14.3～20.0MPa after the reduction.
27, according to the described a kind of Cu-contained catalyst of claim 26, it is characterized in that consisting of of described catalyst: cupric oxide 30%～60%, helping catalyst component is 10%～45%, aluminium oxide is 10%～30%, 0.3%～3.0% alkali metal oxide, before the average crushing strength reduction of catalyst granules is 20.0～28.0MPa, is 14.3～20.0MPa after the reduction.
28,, it is characterized in that described alkali metal oxide is one or more in lithium, sodium, potassium, rubidium, the caesium oxide according to claim 26 or 27 described a kind of Cu-contained catalysts.
29,, it is characterized in that the described catalyst component oxide that helps is in zinc, magnesium, chromium, manganese, iron, the calcium oxide one or more according to claim 26 or 27 described a kind of Cu-contained catalysts.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE3837308A1 (en) * | 1988-11-03 | 1990-05-10 | Basf Ag | COPPER-CONTAINING CATALYST FOR TEMPERATURE CONVERSION |
| DE4244273A1 (en) * | 1992-12-28 | 1994-06-30 | Hoechst Ag | copper catalyst |
| CN1081082C (en) * | 1995-06-28 | 2002-03-20 | 中国科学院大连化学物理研究所 | Aldose hydrogenating process and catalyst for producing sugar alcohol |
| CN1219445A (en) * | 1998-11-16 | 1999-06-16 | 天津大学 | New synthetic copper methoxide series catalysts and their preparation method |
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