CN104307553B - A kind of preparation method of wide temperature rare earth based composite oxides denitrating catalyst - Google Patents
A kind of preparation method of wide temperature rare earth based composite oxides denitrating catalyst Download PDFInfo
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- CN104307553B CN104307553B CN201410467859.3A CN201410467859A CN104307553B CN 104307553 B CN104307553 B CN 104307553B CN 201410467859 A CN201410467859 A CN 201410467859A CN 104307553 B CN104307553 B CN 104307553B
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Abstract
The invention discloses a kind of preparation method of wide temperature rare earth based composite oxides denitrating catalyst, taking titanium dioxide, montmorillonite as carrier, taking ammonium metatungstate, ammonium metavanadate, cerous nitrate, manganese oxide as active component, under auxiliary material is followed, make through mixing, old, kneading, moulding, dry and roasting; Wherein said auxiliary material comprises monoethanolamine, citric acid, ammoniacal liquor, lactic acid, stearic acid, glass fibre, wood pulp, hydroxypropyl methylcellulose, polyethylene glycol oxide, citric acid and water. The present invention adopts complex rare-earth oxidate containing valuable metal as active component, has shortened the soak time of catalyst, has effectively controlled SO2/SO3Conversion ratio, improve the temperature adaptive capacity of catalyst, make the serviceability temperature expanded range of catalyst, in original 320-400 DEG C, expand 150-420 DEG C to, denitration efficiency is more than 90%, in the time that boiler is started shooting, when denitration regional temperature reaches 150 DEG C, just can spray ammonia and carry out denitration operation like this.
Description
Technical field
The present invention relates to a kind of ceramic honeycomb catalyst in environmental protection technical field; a specifically preparation method for wide temperature rare earth based composite oxides denitrating catalyst, the product that adopts the method to prepare is specially adapted to the field clarifying smokes such as thermal power plant, glass factory, chemical plant.
Background technology
For denitrating flue gas, the technology of maturation is SCR method denitration technology the most in the world at present. Denitrating catalyst is the core of whole denitrating system, and SCR denitration technology is by the NOx in flue gas and sprays into the reducing agent (NH in flue gas3) fully mix, in 320-400 DEG C of temperature ranges, under the effect of denitrating catalyst, there is reduction reaction, generate N2And H2O。
This denitrating catalyst is in the time that boiler is opened, if when denitration reaction regional temperature is following lower than 300 DEG C, just can not spray ammonia, otherwise can make sulfur trioxide and ammonia react, generate sulphur ammonium salt and be attached on catalyst surface and equipment, thereby cause catalyst poisoning and equipment corrosion, obstruction. If do not spray ammonia, boiler is in the time of operation in this time so, and nitrogen oxide will discharge beyond standards, causes environmental pollution. Will cause thermal sintering to catalyst if temperature exceedes 400 DEG C, make catalyst permanent failure.
Summary of the invention
The object of the invention is the problem of the existence in order to solve prior art existence, propose a kind of preparation method of wide temperature rare earth based composite oxides denitrating catalyst. Catalyst prepared by the present invention adopts complex rare-earth oxidate containing valuable metal as active component, has shortened the soak time of catalyst, has effectively controlled SO2/SO3Conversion ratio, improve the temperature adaptive capacity of catalyst, made the serviceability temperature expanded range of catalyst, in original 320-400 DEG C, expanded 150-420 DEG C to, in the time that boiler is started shooting, when denitration regional temperature reaches 150 DEG C, just can spray ammonia and carry out denitration operation like this.
Technical scheme of the present invention comprises:
A kind of preparation method of wide temperature rare earth based composite oxides denitrating catalyst, taking titanium dioxide (titanium dioxide), montmorillonite as carrier, taking ammonium metatungstate, ammonium metavanadate, cerous nitrate, manganese oxide as active component, under auxiliary material is followed, make through mixing, old, kneading, moulding, dry and roasting; Wherein said auxiliary material comprises monoethanolamine, citric acid, ammoniacal liquor, lactic acid, stearic acid, glass fibre, wood pulp, hydroxypropyl methylcellulose, polyethylene glycol oxide, citric acid and water.
Such scheme further comprises:
(1) preparation of active component: the water of 45-55kg is added to dissolving tank, the monoethanolamine of 8-12kg is joined in dissolving tank, when temperature arrives 85-95 DEG C, the ammonium metavanadate of 6-10kg is joined in dissolving tank and stirred, again the manganese oxide of the ammonium metatungstate of 30-40kg and 8-12kg is joined in dissolving tank and uniform stirring, until all dissolve and make ammonium metatungstate, ammonium metavanadate living solution;
45-55 premium on currency is added to active dissolution tank, the citric acid of 5-7kg is joined in dissolving tank and stirred, then 4-6kg cerous nitrate is added in dissolving tank until completely dissolved, make cerous nitrate living solution;
(2) mixing process:
Once mixing: the montmorillonite of the titanium dioxide of 350-400 ㎏, 30-40kg is added in batch mixer; Again the lactic acid of the stearic acid of 2-3 ㎏, 6-7kg, 210-250 premium on currency and 40-50 being risen to ammoniacal liquor adds in batch mixer and evenly mixes successively;
Secondary is mixing: by the titanium dioxide of 95-115 ㎏, 16-20 premium on currency and 45-55 rise ammonium metatungstate, ammonium metavanadate living solution adds in batch mixer and evenly mixes;
Three times mixing: the titanium dioxide of 120-150kg and 6-10 are risen to ammoniacal liquor and add in batch mixer and evenly mix, control temperature 85-95 DEG C in batch mixer;
Four times mixing: the glass fibre of the wood pulp of 3.0-3.5kg, 30-40kg and 45-55 are risen to cerous nitrate living solution and add in batch mixer and evenly mix;
Five times mixing: below temperature in batch mixer is down to 70 DEG C time, the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 2-3kg and 2.0-2.3kg is added in batch mixer and evenly mixed;
Six times mixing: the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 4-5kg, 2.0-2.3kg and 4-6 are risen to ammoniacal liquor and add batch mixer evenly to mix, raw material mixes complete;
(3) pH value of raw material after fully mixing is between 7.0-8.0, and moisture control is 28.0-30.0%;
(4) raw material mixing seals and is placed on 20-30 DEG C of temperature, humidity is carried out old in 50.0-70.0% environment;
(5) raw material after old filters and fully kneading, moulding, dry;
(6) product being dried is with entering roasting, and roasting heating curve is parabola, and maximum temperature is 530-550 DEG C, and product kiln discharge temperature is 60-80 DEG C, and roasting time is controlled at 20-40 hour.
Such scheme further comprises:
(1) preparation of active component: the water of 45-55kg is added to dissolving tank, the monoethanolamine of 8-12kg is joined in dissolving tank, when temperature arrives 85-95 DEG C, the ammonium metavanadate of 6-10kg is joined to uniform stirring 10-20 minute in dissolving tank, again the manganese oxide interval of the ammonium metatungstate of 30-40kg and 8-12kg is joined in dissolving tank for 8-12 minute and uniform stirring 30-50 minute, until all dissolve and make ammonium metatungstate, ammonium metavanadate living solution;
45-55 premium on currency is added to active dissolution tank, the citric acid of 5-7kg is joined to uniform stirring 4-6 minute in dissolving tank, then 4-6kg cerous nitrate is added in dissolving tank until completely dissolved, make cerous nitrate living solution;
(2) mixing process:
Once mixing: the montmorillonite of the titanium dioxide of 350-400 ㎏, 30-40kg is added in batch mixer; The lactic acid of the stearic acid of 2-3 ㎏, 6-7kg, 210-250 premium on currency and 40-50 being risen to ammoniacal liquor adds successively and in batch mixer, evenly mixes 15-25 minute again;
Secondary is mixing: the titanium dioxide of 95-115 ㎏, 16-20 premium on currency and 45-55 are risen to ammonium metatungstate, ammonium metavanadate living solution and add and in batch mixer, evenly mix 15-25 minute;
Three times mixing: the titanium dioxide of 120-150kg and 6-10 are risen to ammoniacal liquor and add in batch mixer and evenly mix, control temperature 85-95 DEG C in batch mixer, discharge the gas that raw material produces, after mixing end for the third time, raw material moisture content is controlled at 26.0-28.50%;
Four times mixing: the glass fibre of the wood pulp of 3.0-3.5kg, 30-40kg and 45-55 are risen to cerous nitrate living solution and add and in batch mixer, evenly mix 10-20 minute;
Five times mixing: temperature in batch mixer is down to 70 DEG C when following, the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 2-3kg and 2.0-2.3kg is added and in batch mixer, evenly mixes 7-12 minute;
Six times mixing: the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 4-5kg, 2.0-2.3kg and 4-6 are risen to ammoniacal liquor and add batch mixer evenly to mix 7-12 minute, raw material mixes complete;
(3) pH value of raw material after fully mixing is between 7.0-8.0, and moisture control is 28.0-30.0%; If pH value is lower than 7.0, add ammoniacal liquor to regulate at the 6th time in mixing so;
(4) raw material mixing seals and is placed on 20-30 DEG C of temperature, humidity is carried out old in 50.0-70.0% environment;
(5) raw material after old filters and fully mediates;
(6) raw material that filters and fully mediate carries out old again, and the old time is at 12-24 hour;
(7) raw material of secondary after old, through Powerful extruder extrusion molding, is dried after packaging; Dry be divided into primary drying and redrying, primary drying environment temperature is 20-60 DEG C, and dry environment humidity is 85-10%, start by high humidity low temperature to low humidity high temperature, drying time 2-12 days; Redrying environment temperature is 57-60 DEG C, 24-48 hours drying times;
(8) initial product being dried is with entering roasting, and roasting heating curve is parabola, is started into product by room temperature, and maximum temperature is 530-550 DEG C, and temperature reduces gradually backward, and product kiln discharge temperature is 60-80 DEG C, and roasting time is controlled at 20-40 hour.
The prioritization scheme of such scheme comprises:
(1) active component preparation: the water of 50kg is added to active dissolution tank; Again the monoethanolamine of 9kg is joined in dissolving tank, when temperature arrives 90 DEG C, the ammonium metavanadate of 8kg is joined in dissolving tank and stirred 15 minutes, again the manganese oxide of the ammonium metatungstate of 35kg and 10kg is joined in dissolving tank, 10 minutes, joining day interval, uniform stirring 40 minutes, until all dissolve and make ammonium metatungstate, ammonium metavanadate living solution;
50 premium on currency are added to active dissolution tank, the citric acid of 6kg is joined in dissolving tank, stir after 5 minutes, 5kg cerous nitrate is added in dissolving tank until completely dissolved, make cerous nitrate living solution;
(2) mixing process:
Once mixing: the montmorillonite of the titanium dioxide of 369.5 ㎏, 35kg is added in batch mixer; Again the lactic acid of the stearic acid of 2.6 ㎏, 6.5kg, 230 premium on currency and 45 liters of ammoniacal liquor are added successively in batch mixer and carry out evenly mixing 20 minutes;
Secondary is mixing: the titanium dioxide of 105 ㎏, 18 premium on currency and 50 liters of ammonium metatungstates, ammonium metavanadate living solutions are added in batch mixer and carry out evenly mixing 20 minutes;
Three times mixing: the titanium dioxide of 135kg and 8 liters of ammoniacal liquor are added in batch mixer and evenly mixed, until temperature arrives 90 DEG C of left and right in batch mixer; In batch mixing process for the third time, when material temperature reaches 90 DEG C, discharge the gas that raw material produces, after mixing end for the third time, raw material moisture content is controlled at 26.0-28.50%;
Four times mixing: the glass fibre of the wood pulp of 3.25kg, 36kg and 50 liters of cerous nitrate living solutions are added in batch mixer and carry out evenly mixing 15 minutes;
Five times mixing: below temperature in batch mixer is down to 70 DEG C time, the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 2.44kg and 2.14kg is added in batch mixer and carries out evenly mixing 10 minutes;
Six times mixing: add batch mixer to carry out evenly mixing 10 minutes the polyethylene glycol oxide of the hydroxypropyl methylcellulose of .44kg, 2.14kg and 5 liters of ammoniacal liquor;
(3) pH value of raw material after fully mixing be between 7.0-8.0, and moisture control is 28.0-30.0%, if pH value, lower than 7.0, adds ammoniacal liquor to regulate at the 6th time in mixing so;
(4) the raw material sealing mixing is placed on 20-30 DEG C of temperature, humidity and in 50.0-70.0% environment, carries out oldly, and the time was at 12-24 hours;
(5) raw material after old, through filter and pre-extruder, filters and fully kneading raw material;
(6) raw material, after filter and pre-extruder processing, carries out old 12-24 hour again;
(7) raw material of secondary after old, through Powerful extruder extrusion molding, is dried after packaging;
(8) be dryly divided into primary drying and redrying, primary drying environment temperature is 20-60 DEG C, and dry environment humidity is 85-10%, starts by high humidity low temperature to low humidity high temperature 10 days drying times; Redrying environment temperature is 57-60 DEG C, 24-48 hours drying times;
(9) initial product being dried is carried out roasting, and roasting kiln is continuous mesh belt type kiln, has 12 temperature control points and 13 temperature to show point, and 25 temperature show point altogether; Roasting heating curve is parabola, is started into product by room temperature, and maximum temperature is 530-550 DEG C, and temperature can reduce gradually backward, and product kiln discharge temperature is 60-80 DEG C, and roasting time is controlled at 30 hours.
Technique effect of the present invention is mainly reflected in:
The present invention adopts complex rare-earth oxidate containing valuable metal as active component, has shortened the soak time of catalyst, has effectively controlled SO2/SO3Conversion ratio, improve the temperature adaptive capacity of catalyst, make the serviceability temperature expanded range of catalyst, in original 320-400 DEG C, expand 150-420 DEG C to, denitration efficiency is more than 90%, in the time that boiler is started shooting, when denitration regional temperature reaches 150 DEG C, just can spray ammonia and carry out denitration operation like this.
Conventional catalyst in use, needs 8-12 hour when temperature reaches 300 DEG C in the time of opening of device, reach before 300 DEG C in temperature, can not spray ammonia and carry out denitration, just cause environmental protection discharge beyond standards, if avoid discharge beyond standards, must transform boiler, thereby increase cost and difficulty of construction. And wide temperature catalyst of the present invention is in use, when opening of device, start-up temperature, more than 150 DEG C, so just can be sprayed along with the unlatching of equipment ammonia and carry out denitration, so just realize and save boiler improvement expense, but also the object of qualified discharge. This wide temperature catalyst is applicable to the denitration under low temperature, hot environment flue gas condition.
Detailed description of the invention
Embodiment 1:
A kind of preparation method of wide temperature rare earth based composite oxides denitrating catalyst, taking titanium dioxide, montmorillonite as carrier, taking ammonium metatungstate, ammonium metavanadate, cerous nitrate, manganese oxide as active component, under auxiliary material is followed, make through mixing, old, kneading, moulding, dry and roasting; Wherein said auxiliary material comprises monoethanolamine, citric acid, ammoniacal liquor, lactic acid, stearic acid, glass fibre, wood pulp, hydroxypropyl methylcellulose, polyethylene glycol oxide, citric acid and water.
Concrete scheme comprises:
(1) preparation of active component: the water of 45kg is added to dissolving tank, the monoethanolamine of 8kg is joined in dissolving tank, when temperature arrives 85 DEG C, the ammonium metavanadate of 6kg is joined in dissolving tank and stirred, again the manganese oxide of the ammonium metatungstate of 30kg and 8kg is joined in dissolving tank and uniform stirring, until all dissolve and make ammonium metatungstate, ammonium metavanadate living solution;
45 premium on currency are added to active dissolution tank, the citric acid of 5kg is joined in dissolving tank and stirred, then 4kg cerous nitrate is added in dissolving tank until completely dissolved, make cerous nitrate living solution;
(2) mixing process:
Once mixing: the montmorillonite of the titanium dioxide of 350 ㎏, 30kg is added in batch mixer; Again the lactic acid of the stearic acid of 2 ㎏, 6kg, 210 premium on currency and 40 liters of ammoniacal liquor are added in batch mixer and evenly mixed successively;
Secondary is mixing: the titanium dioxide of 95 ㎏, 16 premium on currency and 45 liters of ammonium metatungstates, ammonium metavanadate living solutions are added in batch mixer and evenly mixed;
Three times mixing: the titanium dioxide of 120kg and 6 liters of ammoniacal liquor are added in batch mixer and evenly mixed, control in batch mixer 85 DEG C of temperature;
Four times mixing: the glass fibre of the wood pulp of 3.0kg, 30kg and 45 liters of cerous nitrate living solutions are added in batch mixer and evenly mixed;
Five times mixing: below temperature in batch mixer is down to 70 DEG C time, the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 2kg and 2.0kg is added in batch mixer and evenly mixed;
Six times mixing: add batch mixer evenly to mix the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 4kg, 2.0kg and 4 liters of ammoniacal liquor, raw material mixes complete;
(3) pH value of raw material after fully mixing is between 7.0-8.0, and moisture control is 28.0-30.0%;
(4) the raw material sealing mixing is placed on 20-30 DEG C of temperature, humidity is carried out old in 50.0-70.0% environment;
(5) raw material after old filters and fully kneading, moulding, dry;
(6) product being dried is with entering roasting, and roasting heating curve is parabola, and maximum temperature is 530 DEG C, and product kiln discharge temperature is 60 DEG C, and roasting time is controlled at 40 hours.
Embodiment 2:
(1) preparation of active component: the water of 55kg is added to dissolving tank, the monoethanolamine of 12kg is joined in dissolving tank, when temperature arrives 95 DEG C, the ammonium metavanadate of 10kg is joined in dissolving tank to uniform stirring 20 minutes, again the manganese oxide interval of the ammonium metatungstate of 40kg and 12kg is joined for 12 minutes in dissolving tank and uniform stirring 50 minutes, until all dissolve and make ammonium metatungstate, ammonium metavanadate living solution;
55 premium on currency are added to active dissolution tank, the citric acid of 7kg is joined in dissolving tank to uniform stirring 6 minutes, then 6kg cerous nitrate is added in dissolving tank until completely dissolved, make cerous nitrate living solution;
(2) mixing process:
Once mixing: the montmorillonite of the titanium dioxide of 400 ㎏, 40kg is added in batch mixer; Again the lactic acid of the stearic acid of 3 ㎏, 7kg, 250 premium on currency and 50 liters of ammoniacal liquor are added successively in batch mixer and carry out evenly mixing 25 minutes;
Secondary is mixing: the titanium dioxide of 115 ㎏, 20 premium on currency and 55 liters of ammonium metatungstates, ammonium metavanadate living solutions are added in batch mixer and carry out evenly mixing 25 minutes;
Three times mixing: the titanium dioxide of 150kg and 10 liters of ammoniacal liquor are added in batch mixer and evenly mixed, control in batch mixer 95 DEG C of temperature, discharge the gas that raw material produces, after mixing end for the third time, raw material moisture content is controlled at 26.0-28.50%;
Four times mixing: the glass fibre of the wood pulp of 3.5kg, 40kg and 55 liters of cerous nitrate living solutions are added in batch mixer and carry out evenly mixing 20 minutes;
Five times mixing: below temperature in batch mixer is down to 70 DEG C time, the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 3kg and 2.3kg is added in batch mixer and carries out evenly mixing 12 minutes;
Six times mixing: add batch mixer to carry out evenly mixing 12 minutes the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 5kg, 2.3kg and 6 liters of ammoniacal liquor, raw material mixes complete;
(3) pH value of raw material after fully mixing is between 7.0-8.0, and moisture control is 28.0-30.0%; If pH value is lower than 7.0, add ammoniacal liquor to regulate at the 6th time in mixing so;
(4) the raw material sealing mixing is placed on 20-30 DEG C of temperature, humidity is carried out old in 50.0-70.0% environment;
(5) raw material after old filters and fully mediates;
(6) raw material that filters and fully mediate carries out old again, and the old time is at 12-24 hour;
(7) raw material of secondary after old, through Powerful extruder extrusion molding, is dried after packaging; Dry be divided into primary drying and redrying, primary drying environment temperature is 60 DEG C, and dry environment humidity is 10%, starts by high humidity low temperature to low humidity high temperature 4 days drying times; Redrying environment temperature is 57 DEG C, 48 hours drying times;
(8) initial product being dried is with entering roasting, and roasting heating curve is parabola, is started into product by room temperature, and maximum temperature is 550 DEG C, and temperature reduces gradually backward, and product kiln discharge temperature is 80 DEG C, and roasting time is controlled at 20 hours.
Exemplary embodiments 3:
A kind of preparation method of wide temperature rare earth based composite oxides denitrating catalyst is taking titanium dioxide (titanium dioxide) and montmorillonite as carrier, with active component W/Mu-V-Ce(tungsten/manganese-vanadium-cerium), make through mixing, kneading, old, moulding, dry, roasting.
Raw material is prepared:
Support material, takes the titanium dioxide (being divided into three parts is: 369.5 ㎏, 105 ㎏, 135 ㎏) of 644.5kg, takes the montmorillonite of 35kg.
Active component raw material: the manganese oxide that takes ammonium metavanadate, 5kg cerous nitrate and the 10kg of ammonium metatungstate, the 8kg of 35kg; Take the monoethanolamine solution of 9kg, the citric acid of 6kg.
Active component preparation: the water of 50kg is added to active dissolution tank; Again the monoethanolamine of 9kg is joined in dissolving tank, when temperature arrives 90 DEG C, the ammonium metavanadate of 8kg is joined in dissolving tank and stirred 15 minutes, again the manganese oxide of the ammonium metatungstate of 35kg and 10kg is joined in dissolving tank, 10 minutes, joining day interval, uniform stirring 40 minutes, until all dissolve and make ammonium metatungstate, ammonium metavanadate living solution, is finally adjusted into liquor capacity 50 liters;
50 premium on currency are added to active dissolution tank, the citric acid of 6kg is joined in dissolving tank, stir after 5 minutes, 5kg cerous nitrate is added in dissolving tank until completely dissolved, make cerous nitrate living solution, finally liquor capacity is adjusted into 50 liters.
Mixing process:
Once mixing: the montmorillonite of the titanium dioxide of 369.5 ㎏, 35kg is added in batch mixer; Again the lactic acid of the stearic acid of 2.6 ㎏, 6.5kg, 230 premium on currency and 45 liters of ammoniacal liquor are added successively in batch mixer and carry out evenly mixing 20 minutes;
Secondary is mixing: the titanium dioxide of 105 ㎏, 18 premium on currency and 50 liters of ammonium metatungstates, ammonium metavanadate living solutions are added in batch mixer and carry out evenly mixing 20 minutes;
Three times mixing: the titanium dioxide of 135kg and 8 liters of ammoniacal liquor are added in batch mixer and evenly mixed, until temperature arrives 90 DEG C of left and right in batch mixer;
Four times mixing: the glass fibre of the wood pulp of 3.25kg, 36kg and 50 liters of cerous nitrate living solutions are added in batch mixer and carry out evenly mixing 15 minutes;
Five times mixing: below temperature in batch mixer is down to 70 DEG C time, the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 2.44kg and 2.14kg is added in batch mixer and carries out evenly mixing 10 minutes;
Six times mixing: add batch mixer to carry out evenly mixing 10 minutes the polyethylene glycol oxide of the hydroxypropyl methylcellulose of .44kg, 2.14kg and 5 liters of ammoniacal liquor, raw material mixes complete.
PH value after raw material fully mixes is between 7.0-8.0, if pH value, lower than 7.0, adds ammoniacal liquor to regulate at the 6th time in mixing so.
In batch mixing process for the third time, when material temperature reaches 90 DEG C, discharge the gas that raw material produces, after mixing end for the third time, raw material moisture content is controlled at 26.0-28.50%.
All mixing complete moisture control is about 28.0-30.0% for raw material, and pH value is controlled at 7.0-8.0.
The raw material mixing seals, and is placed on 20-30 DEG C of temperature, humidity and in 50.0-70.0% environment, carries out oldly, and the time was at 12-24 hours.
Raw material after old, through filter and pre-extruder, filters and fully kneading raw material, impurity in its raw material is filtered with pug and evenly mixes.
Raw material, after filter and pre-extruder processing, is carrying out the old time at 12-24 hour.
Raw material after secondary is old, through the moulding of Powerful extruder basis, enters primary drying after good with packed in cases.
Dry be divided into primary drying and redrying, primary drying environment temperature is 20-60 DEG C, and dry environment humidity is 85-10%, starts by high humidity low temperature to low humidity high temperature 10 days drying times. Redrying environment temperature is 57-60 DEG C, 24-48 hours drying times.
The initial product being dried can enter calcination steps at any time, this product roasting kiln is continuous mesh belt type kiln, this kiln overall length is 52 meters, guipure is 316L track structure, there are 12 temperature control points, show point with 13 temperature, 25 temperature show point, the temperature in conveniently adjusted each region altogether. Heating curve is parabola, is started into product by room temperature, and maximum temperature is 530-550 DEG C, and temperature can reduce gradually backward, and product kiln discharge temperature is 60-80 DEG C, and roasting time is controlled at 30 hours.
Claims (2)
1. the preparation method of one kind wide temperature rare earth based composite oxides denitrating catalyst, taking titanium dioxide, montmorillonite as carrier, taking ammonium metatungstate, ammonium metavanadate, cerous nitrate, manganese oxide as active component, under auxiliary material is followed, make through mixing, old, kneading, moulding, dry and roasting; Wherein said auxiliary material comprises monoethanolamine, citric acid, ammoniacal liquor, lactic acid, stearic acid, glass fibre, wood pulp, hydroxypropyl methylcellulose, polyethylene glycol oxide and water, it is characterized in that:
(1) preparation of active component: the water of 45-55kg is added to dissolving tank, the monoethanolamine of 8-12kg is joined in dissolving tank, when temperature arrives 85-95 DEG C, the ammonium metavanadate of 6-10kg is joined in dissolving tank and stirred, again the manganese oxide of the ammonium metatungstate of 30-40kg and 8-12kg is joined in dissolving tank and uniform stirring, until all dissolve and make ammonium metatungstate, ammonium metavanadate living solution;
45-55 premium on currency is added to active dissolution tank, the citric acid of 5-7kg is joined in dissolving tank and stirred, then 4-6kg cerous nitrate is added in dissolving tank until completely dissolved, make cerous nitrate living solution;
(2) mixing process:
Once mixing: the montmorillonite of the titanium dioxide of 350-400 ㎏, 30-40kg is added in batch mixer; Again the lactic acid of the stearic acid of 2-3 ㎏, 6-7kg, 210-250 premium on currency and 40-50 being risen to ammoniacal liquor adds in batch mixer and evenly mixes successively;
Secondary is mixing: by the titanium dioxide of 95-115 ㎏, 16-20 premium on currency and 45-55 rise ammonium metatungstate, ammonium metavanadate living solution adds in batch mixer and evenly mixes;
Three times mixing: the titanium dioxide of 120-150kg and 6-10 are risen to ammoniacal liquor and add in batch mixer and evenly mix, control temperature 85-95 DEG C in batch mixer;
Four times mixing: the glass fibre of the wood pulp of 3.0-3.5kg, 30-40kg and 45-55 are risen to cerous nitrate living solution and add in batch mixer and evenly mix;
Five times mixing: below temperature in batch mixer is down to 70 DEG C time, the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 2-3kg and 2.0-2.3kg is added in batch mixer and evenly mixed;
Six times mixing: the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 4-5kg, 2.0-2.3kg and 4-6 are risen to ammoniacal liquor and add batch mixer evenly to mix, raw material mixes complete;
(3) the pH value of raw material after fully mixing is between 7.0-8.0, and moisture control is 28.0-30.0%;
(4) raw material mixing seals and is placed on 20-30 DEG C of temperature, humidity is carried out old in 50.0-70.0% environment;
(5) raw material after old filters and fully kneading, moulding, dry;
(6) product being dried is with entering roasting, and roasting heating curve is parabola, and maximum temperature is 550 DEG C, and product kiln discharge temperature is 60-80 DEG C, and roasting time is controlled at 20-40 hour.
2. the preparation method of wide temperature rare earth based composite oxides denitrating catalyst according to claim 1, is characterized in that:
(1) preparation of active component: the water of 45-55kg is added to dissolving tank, the monoethanolamine of 8-12kg is joined in dissolving tank, when temperature arrives 85-95 DEG C, the ammonium metavanadate of 6-10kg is joined to uniform stirring 10-20 minute in dissolving tank, again the manganese oxide interval of the ammonium metatungstate of 30-40kg and 8-12kg is joined in dissolving tank for 8-12 minute and uniform stirring 30-50 minute, until all dissolve and make ammonium metatungstate, ammonium metavanadate living solution;
45-55 premium on currency is added to active dissolution tank, the citric acid of 5-7kg is joined to uniform stirring 4-6 minute in dissolving tank, then 4-6kg cerous nitrate is added in dissolving tank until completely dissolved, make cerous nitrate living solution;
(2) mixing process:
Once mixing: the montmorillonite of the titanium dioxide of 350-400 ㎏, 30-40kg is added in batch mixer; The lactic acid of the stearic acid of 2-3 ㎏, 6-7kg, 210-250 premium on currency and 40-50 being risen to ammoniacal liquor adds successively and in batch mixer, evenly mixes 15-25 minute again;
Secondary is mixing: the titanium dioxide of 95-115 ㎏, 16-20 premium on currency and 45-55 are risen to ammonium metatungstate, ammonium metavanadate living solution and add and in batch mixer, evenly mix 15-25 minute;
Three times mixing: the titanium dioxide of 120-150kg and 6-10 are risen to ammoniacal liquor and add in batch mixer and evenly mix, control temperature 85-95 DEG C in batch mixer, discharge the gas that raw material produces, after mixing end for the third time, raw material moisture content is controlled at 26.0-28.50%;
Four times mixing: the glass fibre of the wood pulp of 3.0-3.5kg, 30-40kg and 45-55 are risen to cerous nitrate living solution and add and in batch mixer, evenly mix 10-20 minute;
Five times mixing: temperature in batch mixer is down to 70 DEG C when following, the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 2-3kg and 2.0-2.3kg is added and in batch mixer, evenly mixes 7-12 minute;
Six times mixing: the polyethylene glycol oxide of the hydroxypropyl methylcellulose of 4-5kg, 2.0-2.3kg and 4-6 are risen to ammoniacal liquor and add batch mixer evenly to mix 7-12 minute, raw material mixes complete;
(3) the pH value of raw material after fully mixing is between 7.0-8.0, and moisture control is 28.0-30.0%; If pH value is lower than 7.0, add ammoniacal liquor to regulate at the 6th time in mixing so;
(4) raw material mixing seals and is placed on 20-30 DEG C of temperature, humidity is carried out old in 50.0-70.0% environment;
(5) raw material after old filters and fully mediates;
(6) raw material that filters and fully mediate carries out old again, and the old time is at 12-24 hour;
(7) raw material of secondary after old, through Powerful extruder extrusion molding, is dried after packaging; Dry be divided into primary drying and redrying, primary drying environment temperature is 20-60 DEG C, and dry environment humidity is 85-10%, start by high humidity low temperature to low humidity high temperature, drying time 2-12 days; Redrying environment temperature is 57-60 DEG C, 24-48 hours drying times;
(8) initial product being dried is with entering roasting, and roasting heating curve is parabola, is started into product by room temperature, and maximum temperature is 550 DEG C, and temperature reduces gradually backward, and product kiln discharge temperature is 60-80 DEG C, and roasting time is controlled at 20-40 hour
。
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| CN105126824A (en) * | 2015-08-21 | 2015-12-09 | 无锡华光新动力环保科技股份有限公司 | Low-temperature manganese-based composite oxide denitration catalyst and preparation method thereof |
| CN106492790A (en) * | 2016-09-23 | 2017-03-15 | 河北工业大学 | A kind of low temperature SCR denitration catalyst and preparation method thereof |
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| CN108993482A (en) * | 2018-08-28 | 2018-12-14 | 河南康宁特环保科技股份有限公司 | A kind of denitrating catalyst and the preparation method and application thereof |
| CN109589986B (en) * | 2018-12-20 | 2022-01-11 | 中国科学院青岛生物能源与过程研究所 | Montmorillonite and titanium dioxide composite carrier loaded active ingredient catalyst, preparation and application |
| CN110639501A (en) * | 2019-11-06 | 2020-01-03 | 山东博霖环保科技发展有限公司 | SCR denitration catalyst and preparation method thereof |
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