CN105562018A - Catalyst for preparing furfuryl alcohol through furfural gas-phase hydrogenation and preparing method - Google Patents

Catalyst for preparing furfuryl alcohol through furfural gas-phase hydrogenation and preparing method Download PDF

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CN105562018A
CN105562018A CN201410551163.9A CN201410551163A CN105562018A CN 105562018 A CN105562018 A CN 105562018A CN 201410551163 A CN201410551163 A CN 201410551163A CN 105562018 A CN105562018 A CN 105562018A
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catalyst
cuo
precursor
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phase hydrogenation
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CN105562018B (en
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朱跃辉
冯海强
赵开径
高继东
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

The invention discloses a catalyst for preparing furfuryl alcohol through furfural gas-phase hydrogenation and a preparing method. The catalyst is prepared from CuO, Cr2O3, La2O3, BaO and SiO2, wherein the molar ratios of CuO to Cr2O3, CuO to La2O3, CuO to BaO and CuO to SiO2 are (1-5), (50-300), (5-30) and (1-10) respectively. The method includes the steps that the catalyst for preparing furfuryl alcohol through furfural gas-phase hydrogenation is prepared from the components according to the use amount by adopting a coprecipitation method. The catalyst has the following advantages that the catalyst is high in activity and selectivity, the furfural conversion rate is 100%, and furfuryl alcohol selectivity is larger than or equal to 98%; the catalyst is long in service life, within the 1000 h of catalyst operation, the furfural conversion rate is 100%, and furfuryl alcohol selectivity is 98.2%; catalyst loads are large, and the liquid hourly space velocity is 0.8-1 h. The catalyst has industrial application performance.

Description

A kind of alduronic gas-phase hydrogenation to prepare alditol catalyst and preparation method
Technical field
The present invention relates to a kind of furfuryl alcohol production field, say further, relate to a kind of alduronic gas-phase hydrogenation to prepare alditol catalyst and preparation method.
Background technology
Furfuryl alcohol is a kind of important industrial chemicals, and furfuryl alcohol can obtain second phthalein propionic acid through hydrolysis, is the intermediate of nutrient drug calcium levulinate; Take furfuryl alcohol as furan type resin, furfuryl alcohol-Lauxite and the phenolic resins etc. that raw material can produce better performances; Furfuryl alcohol is again furane resins, varnish, the good solvent of pigment and rocket fuel; In addition, furfuryl alcohol is also widely used in synthetic fibers, rubber, agricultural chemicals and foundary industry.
The production technology of current furfuryl alcohol can be divided into liquid-phase hydrogenatin technique and gas phase hydrogenation technique two kinds, and the latter's security is high, and furfural purity is high, catalyst long service life, is the development trend that furfural hydrogenation produces furfuryl alcohol technique.The catalyst of current furfural hydrogasification producing furancarbinol is mainly divided into copper silicon system and copper chromium system two class, and the two is compared, and the former exists the problem that activity is low and structural stability is poor, the life-span is short, in current industrial practice, mostly adopt copper chromium-based catalysts.
Chinese patent CN1107079A discloses a kind of catalyst compositing range: CuO30-52%, Cr 2o 328-53%, CaO5-15%, and be added with the Cu-Cr catalyst of VIII race and zinc oxide, at reaction temperature 90-170 DEG C, reaction pressure 0.5MPa, under the condition of load 0.1-0.65g furfural/catalyst .g.h, catalyst initial operating stage has higher activity and selectivity, but catalyst operation later stage activity is not good enough.But furfuraldehyde liquid air speed is 0.4-0.5hr -1, the selective 95-97% of furfural conversion ratio 100%, 2-methylfuran.The major defect of this catalyst is that reaction temperature is higher, the easy coking and deactivation of catalyst.
Chinese patent CN1978051A discloses a kind of catalyst compositing range: CuO25-55%, Cr 2o 325-60%, SiO5-9%, the catalyst of other auxiliary agent 1-6%, at reaction temperature 120-150 DEG C, reaction pressure 0.1-0.2MPa, liquid hourly space velocity (LHSV) 0.12h -1condition under, catalyst reflects higher activity and selectivity, but liquid air speed is lower, and does not provide the evaluating data of the operation of long-lasting catalytic.
The catalyst that Chinese patent CN102631930A discloses report consists of: CuO26-50%, Cr 2o 322-40%, Al 2o 30.10-11%, SiO0.10-11%, the catalyst of auxiliary agent 1-15%, at reaction temperature 120-210 DEG C, reaction pressure 0.001-0.0.5MPa, liquid hourly space velocity (LHSV) 0.4-0.6h -1condition under, furfural is up to conversion ratio 100%, but furfuryl alcohol is selective lower, only has 93.5%.
Summary of the invention
For solving produced problem in prior art, the invention provides a kind of alduronic gas-phase hydrogenation to prepare alditol catalyst and preparation method.Catalyst of the present invention overcomes the shortcoming of prior art, has catalyst activity and selectivity high, long service life, the feature that load is large, has possessed commercial Application performance.
Because the reaction temperature of existing Cu-Cr catalyst is higher, easier coking and deactivation.Cause its life-span short.Generally, in the normal operation of industrial catalyst, the inactivation of catalyst is an inevitable phenomenon.The inactivation of catalyst and not exclusively specially the activity of finger inactivation phase catalyst completely lose, be more stationary phase catalyst activity or selective progressively reduction in use.The inactivation of catalyst is a complicated physics and chemistry process.Usually, the reason of inactivation can be divided into following three aspects: activated centre that catalyst carbon deposition etc. cause covers and duct blocks, poisoning, the catalyst heat inactivation of catalyst and sintering, and the inactivation that wherein carbon distribution causes is one of common cause of catalysqt deactivation.For metallic catalyst, although the reaction of catalysis is different, form the mechanism of carbon distribution, quantity and speed different, but along with the increase of carbon distribution, specific area, the aperture and Active sites etc. of catalyst all can decline, when carbon distribution accumulative to a certain degree time catalysqt deactivation, now catalyst regeneration or be replaced with in order to necessity.The present invention sets about from the composition of raw materials of catalyst and preparation method two aspect, have developed a kind of novel alduronic gas-phase hydrogenation to prepare alditol catalyst lowering catalyst carbon deposition speed, extending catalyst life-span.
An object of the present invention is to provide a kind of catalyst of alduronic gas-phase hydrogenation to prepare alditol.
Comprise: CuO, Cr 2o 3, La 2o 3, BaO and SiO 2
CuO/Cr 2o 3mol ratio be 1 ~ 5; Preferably 2.4 ~ 3.0;
CuO/La 2o 3mol ratio be 50 ~ 300; Preferably 100 ~ 150;
The mol ratio of CuO/BaO is 5 ~ 30; Preferably 10 ~ 20;
CuO/SiO 2mol ratio be 1 ~ 10, preferably 1 ~ 5.
The precursor of described cupric oxide is selected from the one in soluble copper salt, preferred copper nitrate, copper sulphate, copper chloride or Schweinfurt green, more preferably copper nitrate;
The initiation material of described chromium oxide is selected from the one in solubility chromic salts, is preferably chromic nitrate, chromium sulfate, chromium chloride, chromic acetate or chromic anhydride, is more preferably chromic anhydride;
The precursor of described lanthana is lanthanum chloride or lanthanum nitrate, is preferably lanthanum nitrate;
Described barytic precursor is barium chloride or barium nitrate, is preferably barium nitrate;
The precursor of described silica is Ludox or waterglass, is preferably Ludox, is more preferably acidic silicasol.
Two of object of the present invention is to provide a kind of preparation method of catalyst of alduronic gas-phase hydrogenation to prepare alditol.
Comprise:
Described component adopts coprecipitation to prepare described alduronic gas-phase hydrogenation to prepare alditol catalyst by described consumption.
Comprise the following steps:
(1) cupric oxide, chromium oxide, the precursor of lanthana and silica is water-soluble obtains mixed solution; Barytic precursor is water-soluble;
(2) add deionized water in reactor, under the condition of 25-40 DEG C, the mixed solution of aqueous slkali and step (1), barytic precursor solution three strands also stream join in reactor, and control ph is 5-8, have been stirred to sediment and have generated;
(3) by the sediment of step (2) after filtration, dry, obtained described catalyst fines after roasting;
Described alkali lye is ammoniacal liquor and/or sal volatile.
Drying in step (3) and roasting can adopt common process conditions in prior art, can be preferred in the present invention: baking temperature is 100-120 DEG C, 10 ~ 20 hours drying times; Sintering temperature is 350 ~ 400 DEG C, and roasting time is 2 ~ 6 hours.
In order to gain in strength and lubricity, in the catalyst fines that can preferably prepare in step (3), add the graphite compression molding of the 0.5 ~ 2wt% accounting for catalyst fines gross weight.
Silica adds with the form of colloidal sol by the present invention, play skeletal support effect, increase specific area and the pore passage structure of catalyst, and cupric oxide, chromium oxide, lanthana and barium monoxide are added by the mode of co-precipitation, form tiny particle, improve the decentralization of active component, and then improve the specific surface area active of per volume of catalyst, finally reach the object in extending catalyst life-span; In addition, add lanthana in the catalyst, because lanthana is alkalescence, the ability of adsorb water vapor is large (containing a small amount of water in furfural), thus make the steam/hydrocarbons ratio of catalyst surface much larger than reaction body mutually in steam/hydrocarbons ratio, this improves the resistive connection charcoal ability of catalyst.
Catalyst prepared by the present invention has higher specific area, is 150 ~ 162m 2/g.Catalyst prepared by the present invention has higher metallic copper decentralization, is 0.55 ~ 0.65.In catalyst sample, the decentralization of Ni metal adopts N 2the chemiadsorption of O measures.Generally speaking, in hydrogenation reaction, the decentralization of active metal component is larger, and its catalytic activity is higher, catalytic life is also longer.
The present invention specifically can by the following technical solutions:
(1) preparation of copper nitrate, chromic acid, lanthanum nitrate and silicon sol solution is according to the mol ratio of component each in catalyst, takes copper nitrate, chromic acid and lanthanum nitrate and silicon sol solution, and miscible in deionized water, barium nitrate is dissolved in deionized water;
(2) appropriate deionized water is put into reactor, under the condition of 25 ~ 40 DEG C, aqueous slkali, mixed solution (copper nitrate, chromic acid, lanthanum nitrate and Ludox) and barium nitrate solution three strands stream is used to join reaction in reactor again, continuous stirring, the pH value controlling reaction is 5 ~ 8, after reinforced, continue to stir 0.5 ~ 5 hour at this temperature, reaction has sediment to generate;
(3) by the sediment of step (2) after filtering, 100-120 DEG C of drying 10 ~ 20 hours, and roasting 2 ~ 6 hours at 350 ~ 400 DEG C, namely the graphite compression molding then adding 0.5wt% ~ 2wt% obtains catalyst.
The present invention compared with prior art tool has the following advantages:
(1) catalyst has higher activity and selectivity, and furfural conversion ratio 100%, 2-methylfuran is selective >=and 98%;
(2) catalyst life is long, is greater than 1000 hours;
(3) load is large, air speed≤0.8h during liquid -1.
Detailed description of the invention
Below in conjunction with embodiment, further illustrate the present invention.
In embodiment raw materials used be commercially available.
Embodiment 1
Take copper nitrate (Cu (NO 3) 23H 2o) 151.g, chromic anhydride (CrO 3) 50.0g, lanthanum nitrate (La (NO 3) 36H 2o) the acidic silicasol mixing of 4.6g, 48g25wt% is dissolved in 1000mL deionized water, same barium nitrate (Ba (NO 3) 2) 12.1g is also dissolved in (CuO/Cr in 1000mL deionized water 2o 3, CuO/La 2o 3, CuO/BaO, CuO/SiO 2mol ratio respectively 2.5; 125; 13.6; 3.125); First 100mL deionized water is put into reactor, under constantly stirring, by the ammoniacal liquor of copper-chromium-lanthanum-silicon mixed liquor, barium nitrate solution and 18wt% and stream add, control pH value in reaction 6, the temperature of reactant liquor is risen to 40 DEG C simultaneously, reinforced complete continuation insulated and stirred 2 hours, filter, 120 DEG C of dryings 12 hours, then in Muffle furnace in 350 DEG C of roastings 4 hours, namely the graphite compression molding then adding 1wt% obtains catalyst.After obtained catalyst, carry out catalyst activity evaluation with following methods: in stainless steel reactor, the preformed catalyst of the present invention is reduced 6 hours with nitrogen hydrogen mixture at 270 DEG C of temperature.At reaction condition be: reaction temperature 110-150 DEG C, pressure 0.3MPa, liquid air speed 0.8hr -1, under the condition of hydrogen aldehyde mol ratio 10, catalyst is in operation 1000 hours, and furfural conversion ratio is 100%, and furfuryl alcohol average selectivity is 99.3%.
Embodiment 2
Take copper nitrate (Cu (NO 3) 23H 2o) 163.1g, chromic anhydride (CrO 3) 50.0g, lanthanum nitrate (La (NO 3) 36H 2o) the acidic silicasol mixing of 4.8g, 41g25wt% is dissolved in 1000mL deionized water, barium nitrate (Ba (NO 3) 2) 12.7g is dissolved in (CuO/Cr in 1000mL deionized water 2o 3, CuO/La 2o 3, CuO/BaO, CuO/SiO 2mol ratio respectively 2.64; 120; 13.5; 3.88); First 100mL deionized water is put into reactor, under constantly stirring, by copper-chromium-lanthanum mixed liquor, barium nitrate solution and with the ammoniacal liquor of 18wt% and stream add, control pH value in reaction 6, the temperature of reactant liquor is risen to 40 DEG C simultaneously, reinforced complete continuation insulated and stirred 2 hours, filter, 120 DEG C of dryings 12 hours, then in Muffle furnace in 350 DEG C of roastings 4 hours, namely the graphite compression molding then adding 1wt% obtains catalyst.After obtained catalyst, carry out catalyst activity evaluation with following methods: in stainless steel reactor, the preformed catalyst of the present invention is reduced 6 hours with nitrogen hydrogen mixture at 270 DEG C of temperature.At reaction condition be: reaction temperature 120 DEG C, pressure 0.3MPa, liquid air speed 0.8hr -1, under the condition of hydrogen aldehyde mol ratio 10, furfural conversion ratio is 100%, and furfuryl alcohol is selective is 99.5%.
Embodiment 3
Take copper nitrate (Cu (NO 3) 23H 2o) 181.2g, chromic anhydride (CrO 3) 50.0g, lanthanum nitrate (La (NO 3) 36H 2o) acidic silicasol of 5.2g, 50g25wt% is miscible in 1000mL deionized water, simultaneously barium nitrate (Ba (NO 3) 2) 13.5g is also dissolved in (CuO/Cr in 1000mL deionized water 2o 3, CuO/La 2o 3, CuO/BaO, CuO/SiO 2mol ratio respectively 3; 125; 14.4; 3.57); First 100mL deionized water is put into reactor, under constantly stirring, by the ammoniacal liquor of copper-chromium-lanthanum mixed liquor, barium nitrate solution and 18wt% and stream add, control pH value in reaction 6, the temperature of reactant liquor is risen to 40 DEG C simultaneously, reinforced complete continuation insulated and stirred 2 hours, filter, 120 DEG C of dryings 12 hours, then in Muffle furnace in 350 DEG C of roastings 4 hours, namely the graphite compression molding of 1wt% obtains catalyst.After obtained catalyst, carry out catalyst activity evaluation with following methods: in stainless steel reactor, the preformed catalyst of the present invention is reduced 6 hours with nitrogen hydrogen mixture at 270 DEG C of temperature.At reaction condition be: reaction temperature 120 DEG C, pressure 0.3MPa, liquid air speed 0.8hr -1, under the condition of hydrogen aldehyde mol ratio 10, furfural conversion ratio is 100%, and furfuryl alcohol is selective is 99.2%.
Embodiment 4
Take copper nitrate (Cu (NO 3) 23H 2o) 151.g, chromic anhydride (CrO 3) 125g, lanthanum nitrate (La (NO 3) 36H 2o) acidic silicasol of 11.5g, 15g25wt% is miscible in 1000mL deionized water; Barium nitrate (Ba (NO simultaneously 3) 2) 32.9g is dissolved in 1000mL deionized water (CuO/Cr 2o 3, CuO/La 2o 3, CuO/BaO, CuO/SiO 2mol ratio respectively 1; 50; 5; 10); First 100mL deionized water is put into reactor, under constantly stirring, by the ammoniacal liquor of copper-chromium-lanthanum-silicon mixed liquor, barium nitrate solution and 18wt% and stream add, control pH value in reaction 6, the temperature of reactant liquor is risen to 40 DEG C simultaneously, reinforced complete continuation insulated and stirred 2 hours, filter, 120 DEG C of dryings 12 hours, then in Muffle furnace in 350 DEG C of roastings 4 hours, namely the graphite compression molding then adding 1wt% obtains catalyst.After obtained catalyst, carry out catalyst activity evaluation with following methods: in stainless steel reactor, the preformed catalyst of the present invention is reduced 6 hours with nitrogen hydrogen mixture at 270 DEG C of temperature.At reaction condition be: reaction temperature 110-150 DEG C, pressure 0.3MPa, liquid air speed 0.8hr -1, under the condition of hydrogen aldehyde mol ratio 10, catalyst is in operation 1000 hours, and furfural conversion ratio is 100%, and furfuryl alcohol average selectivity is 99.0%.
Embodiment 5
Take copper nitrate (Cu (NO 3) 23H 2o) 151g, chromic anhydride (CrO 3) 25.0g, lanthanum nitrate (La (NO 3) 36H 2o) acidic silicasol of 1.92g, 150g25wt% is miscible in 1000mL deionized water; Meanwhile, barium nitrate (Ba (NO 3) 2) 5.5g is dissolved in (CuO/Cr in 1000mL deionized water 2o 3, CuO/La 2o 3, CuO/BaO, CuO/SiO 2mol ratio respectively 5; 300; 30; 1); First 100mL deionized water is put into reactor, under constantly stirring, by the ammoniacal liquor of copper-chromium-lanthanum-silicon mixed liquor, barium nitrate solution and 18wt% and stream add, control pH value in reaction 6, the temperature of reactant liquor is risen to 40 DEG C simultaneously, reinforced complete continuation insulated and stirred 2 hours, filter, 120 DEG C of dryings 12 hours, then in Muffle furnace in 350 DEG C of roastings 4 hours, namely the graphite compression molding then adding 1wt% obtains catalyst.After obtained catalyst, carry out catalyst activity evaluation with following methods: in stainless steel reactor, the preformed catalyst of the present invention is reduced 6 hours with nitrogen hydrogen mixture at 270 DEG C of temperature.At reaction condition be: reaction temperature 110-150 DEG C, pressure 0.3MPa, liquid air speed 0.8hr -1, under the condition of hydrogen aldehyde mol ratio 10, catalyst is in operation 1000 hours, and furfural conversion ratio is 100%, and furfuryl alcohol average selectivity is 98.7%.
Comparative example
Take copper nitrate (Cu (NO 3) 23H 2o) 151.0g, chromic anhydride (CrO 3) 50.0g and lanthanum nitrate (La (NO 3) 36H 2o) 4.6g is miscible in 700mL deionized water, barium nitrate (Ba (NO 3) 2) 12.1g is dissolved in 300mL deionized water; First 100mL deionized water is put into reactor, under constantly stirring, by the ammoniacal liquor of copper-chromium-lanthanum mixed liquor, barium nitrate solution and 18 (wt) % and stream add, control pH value in reaction 6, the temperature of reactant liquor is risen to 40 DEG C simultaneously, reinforced complete continuation insulated and stirred 2 hours, filter, 120 DEG C of dryings 12 hours, then in Muffle furnace in 350 DEG C of roastings 4 hours, obtain catalyst fines sample, it consists of: CuO/Cr 2o 3mol ratio be 2.5, CuO/La 2o 3mol ratio be the mol ratio of 118, CuO/BaO be 13.5, namely the graphite compression molding then adding 1wt% obtains catalyst.After obtained catalyst, carry out catalyst activity evaluation with following methods: in stainless steel reactor, the preformed catalyst of the present invention is reduced 6 hours with nitrogen hydrogen mixture at 220-230 DEG C of temperature.At reaction condition be: reaction temperature 110-150 DEG C, pressure 0.3MPa, liquid air speed 0.8hr -1, under the condition of hydrogen aldehyde mol ratio 10, catalyst is in operation 1000 hours, and furfural conversion ratio is 99.5%, and furfuryl alcohol average selectivity is 98.0%.
Embodiment compares with comparative example
Furfural conversion ratio Furfuryl alcohol average selectivity
Embodiment 1 100% 99.3%
Embodiment 2 100% 99.5%
Embodiment 3 100% 99.2%
Embodiment 4 100% 99.0%
Embodiment 5 100% 98.7%
Comparative example 99.5% 98.0%
As can be seen from the above table, the catalyst of the catalyst synthesized by this patent method and the synthesis of conventional method furfural conversion ratio and furfural selective on obviously there is advantage.Therefore the alduronic gas-phase hydrogenation to prepare alditol catalyst of this patent has novelty and practicality.

Claims (9)

1. an alduronic gas-phase hydrogenation to prepare alditol catalyst, is characterized in that described catalyst comprises:
CuO, Cr 2o 3, La 2o 3, BaO and SiO 2,
CuO/Cr 2o 3mol ratio be 1 ~ 5;
CuO/La 2o 3mol ratio be 50 ~ 300;
The mol ratio of CuO/BaO is 5 ~ 30;
CuO/SiO 2mol ratio be 1 ~ 10.
2. alduronic gas-phase hydrogenation to prepare alditol catalyst as claimed in claim 2, is characterized in that:
CuO/Cr 2o 3mol ratio be 2.4 ~ 3.0;
CuO/La 2o 3mol ratio be 100 ~ 150;
The mol ratio of CuO/BaO is 10 ~ 20;
CuO/SiO 2mol ratio be 1 ~ 5.
3. alduronic gas-phase hydrogenation to prepare alditol catalyst as claimed in claim 1, is characterized in that:
The precursor of described cupric oxide is selected from the one in soluble copper salt;
The initiation material of described chromium oxide is selected from the one in solubility chromic salts.
4. alduronic gas-phase hydrogenation to prepare alditol catalyst as claimed in claim 3, is characterized in that:
The precursor of described cupric oxide is copper nitrate, copper sulphate, copper chloride or Schweinfurt green;
The precursor of described chromium oxide is chromic nitrate, chromium sulfate, chromium chloride, chromic acetate or chromic anhydride;
The precursor of described lanthana is lanthanum chloride or lanthanum nitrate;
Described barytic precursor is barium chloride or barium nitrate;
The precursor of described silica is Ludox or waterglass.
5. alduronic gas-phase hydrogenation to prepare alditol catalyst as claimed in claim 4, is characterized in that:
The precursor of described cupric oxide is copper nitrate; The precursor of described chromium oxide is chromic anhydride; The precursor of described lanthana is lanthanum nitrate; Described barytic precursor is barium nitrate; The precursor of described silica is acidic silicasol.
6. a preparation method for the alduronic gas-phase hydrogenation to prepare alditol catalyst as described in one of Claims 1 to 5, is characterized in that:
Described component adopts coprecipitation to prepare described alduronic gas-phase hydrogenation to prepare alditol catalyst by described consumption.
7. preparation method as claimed in claim 6, is characterized in that described method comprises:
(1) cupric oxide, chromium oxide, the precursor of lanthana and silica is water-soluble obtains mixed solution; Barytic precursor is water-soluble;
(2) add deionized water in reactor, under the condition of 25-40 DEG C, the mixed solution of aqueous slkali and step (1), barytic precursor solution three strands also stream join in reactor, and control ph is 5-8, have been stirred to sediment and have generated;
(3) by the sediment of step (2) after filtration, dry, obtained described catalyst fines after roasting;
Described alkali lye is ammoniacal liquor and/or sal volatile.
8. preparation method as claimed in claim 7, is characterized in that:
The graphite compression molding of the 0.5-2wt% accounting for catalyst fines weight is added in the catalyst fines that step (3) obtains.
9. preparation method as claimed in claim 7, is characterized in that:
In step (3), baking temperature is 100-120 DEG C, 10 ~ 20 hours drying times; Sintering temperature is 350 ~ 400 DEG C, and roasting time is 2 ~ 6 hours.
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