CN1322920C - Petroleum hydrocarbon completely catalyzed oxidative catalyst - Google Patents
Petroleum hydrocarbon completely catalyzed oxidative catalyst Download PDFInfo
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- CN1322920C CN1322920C CNB2005100522021A CN200510052202A CN1322920C CN 1322920 C CN1322920 C CN 1322920C CN B2005100522021 A CNB2005100522021 A CN B2005100522021A CN 200510052202 A CN200510052202 A CN 200510052202A CN 1322920 C CN1322920 C CN 1322920C
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Abstract
The present invention relates to a catalyst I for the complete catalytic oxidation of heavy liquid petroleum hydrocarbon with width components, which is petroleum hydrocarbon C1 to C10. In the preparation, a non-shaped Al2 O3-SiO2 carrier is dipped in mixed solution which is prepared by cerous nitrate, calcium carbonate and barium carbonate and is arranged in a muffle furnace for heating, thermal insulation and natural cooling, and thus, a processed carrier is obtained; the processed carrier is then dipped in mixed liquor which is prepared by manganese nitrate, cobalt nitrate, nickel nitrate and copper nitrate and is arranged in the muffle furnace for heating, thermal insulation and natural cooling, and thus, the catalyst is obtained. The catalyst is approached to complete oxidation under a low temperature, the pollution caused by gas waste of fuel burning is fundamentally eliminated or is greatly reduced, and the waste gas is not negatively processed. Furthermore, because the temperature of the complete oxidation is lower than the burning temperature of flame, the controllability of the reaction is high, and a practical degree can reach. Thus, manufacturing cost is greatly reduced, and the large-scale application of the catalyst can be realized.
Description
Technical field
The present invention relates to a kind of catalyst, be particularly useful for the complete catalyst for catalytic oxidation of wide component liquid condition petroleum hydrocarbon.
Background technology
In the oxidation of hydro carbons, the research of liquid towards hydrocarbon oxidation has also had very long history, but the purpose of former research is to obtain the incomplete oxidation product, the target that complete oxidation is pursued before not being, warp is to domestic and foreign literature and retrieval, and relevant Chinese patent comprises:
The catalyst (application number 00126383.8) that is used for the alkane oxidation;
The method of alkane oxidation (application number 97195087.3);
Low grade paraffine oxidation dehydrogenating catalyst and the method (application number 99106660.X) of producing alkene;
A kind of alkane oxidation catalyst and preparation method thereof (application number 96104766.6).
Have about the representational patent of the catalyst of catalyzing combustion of gasoline:
A kind of additive for catalyzing combustion of gasoline (application number 94112636.6);
A kind of additive for catalyzing combustion of diesel oil (application number 94112635.8);
A kind of oil inflame Preparation of catalysts method (application number 00113356.X);
Combustion catalyst (application number 98803842.0)
These catalyst all are that the form with additive joins and plays catalytic action in the fuel.
Also relevant for the patent of low concentration effumability organic gas completely oxidizing catalyst as:
Catalyst (application number 97192173.3) with full oxidation of volatile organic compounds;
Low concentration C1/C2 organic emission completely oxidizing catalyst and preparation method (application number 00108480.1);
Preparation method of a kind of perovskite type rare-earth compound oxide CO burning catalyst and products thereof and purposes (application number 93120614.6).
Relevant United States Patent (USP) comprises:
Alkane?oxidation?with?porphyrins?and?metal?complexesthereof?having?haloalkyl?side?chains(PAT.NO.5770728)
Catalyst?and?method?for?vapor?phase?oxidation?of?alkanehydrocarbons(PAT.NO.5543532)
New?manganese?catalyst?for?light?alkane?oxidation(PAT.NO.5345011)
Chromia?on?metal?oxide?for?the?oxidation?of?alkane?toalcohol(PAT.NO.5345010)
Alkane?oxidation?catalysts(PAT.NO.5091354)
Alkane?oxidation?process(PAT.NO.4898989)
Alkane?oxidation?catalyst(PAT.NO.4803187)
Method?for?production?of?alcohol，ketone，and?epoxide?byoxidation?of?hydrocarbone(PAT.NO.5623090)
Patent documentation according to existing research background and retrieval is found out, also not with mode and the similar catalyst patent of catalyst of the present invention with the liquefied hydrocarbon complete oxidation.
Under the effect of catalyst of the present invention, wide component petroleum hydrocarbon C1～C10 is completely oxidized to carbon dioxide, water in the ionic state of lower temperature, while is a spot of hydrocarbon CH of by-product and carbon monoxide CO only, because the conversion zone temperature is relatively low, so there is not oxynitrides to produce.Rather than under traditional flame combustion, promptly under the high-temperature plasma attitude, be oxidized to hydrocarbon CH and the carbon monoxide CO and the oxynitrides of the not complete oxidation of carbon dioxide, water and high-load.Under the effect of catalyst of the present invention, the oxidized tail gas of wide component petroleum hydrocarbon C1～C10 has reached fully and has been better than index of correlation in No. 4 standards in Europe of motor vehicle exhaust emission, and the clean utilization of petroleum hydrocarbon fuel commonly used is now had positive effect.
Summary of the invention
The object of the invention is, a kind of complete catalyst for catalytic oxidation of wide component heavy liquid condition petroleum hydrocarbon that is used for of development, and this catalyst is petroleum hydrocarbon C1-C10, in preparation is cerous nitrate, calcium nitrate, barium nitrate to be mixed with mixed solution impregnated in unformed Al
2O
3-SiO
2On the carrier, be positioned over intensification in the muffle furnace, insulation, promptly get the carrier of handling after the cooling naturally; Again manganese nitrate, cobalt nitrate, nickel nitrate, copper nitrate are mixed with mixed liquor and impregnated on the carrier of handling, be positioned over intensification in the muffle furnace, insulation, promptly get catalyst after the cooling naturally.This catalyst with wide component petroleum hydrocarbon C1～C10 under lower temperature near complete oxidation, fundamentally eliminate or reduce the pollution that fuel combustion waste gas causes significantly, rather than negatively handle waste gas.In addition because the temperature of complete oxidation is a lot of than the temperature reduction of flame combustion, so the controllability of reaction improves.Low-cost catalyst is used and is reached the degree of practicality in the petroleum hydrocarbon complete oxidation.This reduces manufacturing cost significantly, makes the large-scale application of this catalyst become possibility.
Full catalytic oxidating of petrolum hyalrocarbon catalyst of the present invention, this catalyst with choose any one kind of them in cerous nitrate, calcium nitrate, three kinds of compounds of barium nitrate or two kinds be mixed with solution impregnation in unformed Al
2O
3-SiO
2On the carrier, be positioned over intensification in the muffle furnace, insulation, promptly get the carrier of handling after the cooling naturally; Again any one or two kinds in manganese nitrate, cobalt nitrate, nickel nitrate, four kinds of compounds of copper nitrate are mixed with solution impregnation on the carrier of handling, are positioned in the muffle furnace and heat up, insulation, promptly get catalyst after cooling off naturally; Containing composition in the gained catalyst is the quality percentage composition: unformed Al
2O
3-SiO
2Carrier 85-95%, the total content 0.9-2.1% of any one or two kinds in manganese oxide, cobalt oxide, nickel oxide, four kinds of compounds of cupric oxide; The total content 4.1-12.9% of any one or two kinds in cerium oxide, calcium oxide, three kinds of compounds of barium monoxide.
Full catalytic oxidating of petrolum hyalrocarbon Preparation of catalysts method follows these steps to carry out:
A, with choose any one kind of them in cerous nitrate, calcium nitrate, the barium nitrate or two kinds be mixed with solution, molal quantity equates when selecting two kinds of compounds for use;
B, mixed solution be impregnated in unformed Al
2O
3-SiO
2On the carrier, after 50-100 ℃ of abundant drying, it is put in slowly is warmed up to 200-300 ℃ in the muffle furnace, be incubated after 2-6 hour to cool off naturally and promptly get the carrier of handling with stove;
C, with choose any one kind of them in manganese nitrate, cobalt nitrate, nickel nitrate, the copper nitrate or two kinds be mixed with solution, impregnated in the unformed Al that the b step process is crossed
2O
3-SiO
2On the carrier, in 50～60 ℃ of abundant dryings, molal quantity equates when wherein selecting two kinds of compounds for use;
D, the unformed Al that the c step process is crossed
2O
3-SiO
2Carrier is put in the muffle furnace, heats up with 100～150 ℃/30 minutes speed, is incubated 1-4 hour after 400-800 ℃, cools off naturally with stove then, promptly gets catalyst.
The full catalytic oxidating of petrolum hyalrocarbon Application of Catalyst is: catalyst is heated to 450～500 ℃ in air, the premix gas of blowing air and gasification lighter hydrocarbons on catalyst, complete oxidation takes place and generates carbon dioxide and water in lighter hydrocarbons on catalyst, its surface temperature reduces by 200～250 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the flame combustion, catalytic bed is kermesinus, does not have flame to produce.
The characteristics that are used for wide component liquid condition petroleum hydrocarbon completely oxidizing catalyst of the present invention are:
Ingredient is all cheap and easy to get in this catalyst, and is cheap for manufacturing cost, is easy to large-scale application.
The air that can will reach flammable concentration is completely oxidized to carbon dioxide and water at a lower temperature with gasification lighter hydrocarbons gaseous mixture.
Liquid light hydrocarbon 100% oxidation that can compositional range is very wide.
Being applied as in the petroleum hydrocarbon complete oxidation: catalyst is heated to 450～500 ℃ in air, the premix gas of blowing air and gasification petroleum hydrocarbon on catalyst, catalytic oxidation takes place and generates carbon dioxide in petroleum hydrocarbon on catalyst, water, while is a small amount of not the hydrocarbon CH and the carbon monoxide CO of complete oxidation of by-product only, emits a large amount of heat simultaneously.The hydrocarbon CH of complete oxidation does not account for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.1%, carbon monoxide CO accounts for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.3%, because the conversion zone temperature is relatively low, so there is not oxynitrides to produce.Air measures than being made into according to chemical reaction with the premix gas of gasification petroleum hydrocarbon, beds was dark red state when petroleum hydrocarbon on catalyst complete oxidation took place, but there is not flame to produce, catalyst surface temperature equates everywhere, petroleum hydrocarbon under catalyst action during by complete oxidation catalyst surface temperature reduce by 200～250 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the normal pressure flame combustion.
The specific embodiment
Embodiment 1
A, cerous nitrate is mixed with solution;
B, cerous nitrate solution be impregnated in unformed Al
2O
3-SiO
2On the carrier, after 50 ℃ of abundant dryings, it is put in slowly is warmed up to 200 ℃ in the muffle furnace, be incubated after 2 hours to cool off naturally and promptly get the carrier of handling with stove;
C, again with the manganese nitrate wiring solution-forming, impregnated in the unformed Al that the b step process is crossed
2O
3-SiO
2On the carrier, fully dry in 50 ℃;
D, the unformed Al that the c step process is crossed
2O
3-SiO
2Carrier is put in the muffle furnace, heats up with 100 ℃/30 minutes speed, is incubated 4 hours after 800 ℃, cools off naturally with stove then, promptly gets catalyst.
Contain composition in the gained catalyst and be (quality percentage composition):
Al
2O
3-SiO
2Carrier 86.2%
Ceria 12.7%
Manganese dioxide 1.1%
Catalyst being applied as in wide component petroleum hydrocarbon C1～C10 complete oxidation: catalyst is heated to 450 ℃ in air, the premix gas of blowing air and gasification petroleum hydrocarbon on catalyst, catalytic oxidation takes place and generates carbon dioxide in petroleum hydrocarbon on catalyst, water, while is a small amount of not the hydrocarbon CH and the carbon monoxide CO of complete oxidation of by-product only, emits a large amount of heat simultaneously.The hydrocarbon CH of complete oxidation does not account for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.1%, carbon monoxide CO accounts for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.3%, because the conversion zone temperature is relatively low, so there is not oxynitrides to produce.Air measures than being made into according to chemical reaction with the premix gas of gasification petroleum hydrocarbon, beds was dark red state when petroleum hydrocarbon on catalyst complete oxidation took place, but there is not flame to produce, catalyst surface temperature equates everywhere, petroleum hydrocarbon under catalyst action during by complete oxidation catalyst surface temperature reduce by 200 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the normal pressure flame combustion.
Embodiment 2
A, calcium nitrate is mixed with solution;
B, calcium nitrate solution be impregnated in unformed Al
2O
3-SiO
2On the carrier, after 55 ℃ of abundant dryings, it is put in slowly is warmed up to 250 ℃ in the muffle furnace, be incubated after 4 hours to cool off naturally and promptly get the carrier of handling with stove;
C, again with the cobalt nitrate wiring solution-forming, impregnated in the unformed Al that the b step process is crossed
2O
3-SiO
2On the carrier, fully dry in 55 ℃;
D, the unformed Al that the c step process is crossed
2O
3-SiO
2Carrier is put in the muffle furnace, heats up with 120 ℃/30 minutes speed, is incubated 3 hours after 600 ℃, cools off naturally with stove then, promptly gets catalyst.
Contain composition in the gained catalyst and be (quality percentage composition):
Al
2O
3-SiO
2Carrier 89.8%
Calcium oxide 8.7%
Cobalt sesquioxide 1.5%
Catalyst being applied as in wide component petroleum hydrocarbon C1～C10 complete oxidation: catalyst is heated to 460 ℃ in air, the premix gas of blowing air and gasification petroleum hydrocarbon on catalyst, catalytic oxidation takes place and generates carbon dioxide in petroleum hydrocarbon on catalyst, water, while is a small amount of not the hydrocarbon CH and the carbon monoxide CO of complete oxidation of by-product only, emits a large amount of heat simultaneously.The hydrocarbon CH of complete oxidation does not account for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.1%, carbon monoxide CO accounts for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.3%, because the conversion zone temperature is relatively low, so there is not oxynitrides to produce.Air measures than being made into according to chemical reaction with the premix gas of gasification petroleum hydrocarbon, beds was dark red state when petroleum hydrocarbon on catalyst complete oxidation took place, but there is not flame to produce, catalyst surface temperature equates everywhere, petroleum hydrocarbon under catalyst action during by complete oxidation catalyst surface temperature reduce by 200 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the normal pressure flame combustion.
Embodiment 3
A, barium nitrate is mixed with solution;
B, with the barium nitrate solution impregnation in unformed Al
2O
3-SiO
2On the carrier, after 60 ℃ of abundant dryings, it is put in slowly is warmed up to 300 ℃ in the muffle furnace, be incubated after 2 hours to cool off naturally and promptly get the carrier of handling with stove;
C, again with the nickel nitrate wiring solution-forming, nickel nitrate be impregnated in the unformed Al that the b step process is crossed
2O
3-SiO
2On the carrier, fully dry in 60 ℃;
D, the unformed Al that the c step process is crossed
2O
3-SiO
2Carrier is put in the muffle furnace, heats up with 150 ℃/30 minutes speed, is incubated 3 hours after 500 ℃, cools off naturally with stove then, promptly gets catalyst.
Contain composition in the gained catalyst and be (quality percentage composition):
Al
2O
3-SiO
2Carrier 87.9%
Barium monoxide 10.4%
Nickel oxide 1.7%
Catalyst being applied as in wide component petroleum hydrocarbon C1～C10 complete oxidation: catalyst is heated to 470 ℃ in air, the premix gas of blowing air and gasification petroleum hydrocarbon on catalyst, catalytic oxidation takes place and generates carbon dioxide in petroleum hydrocarbon on catalyst, water, while is a small amount of not the hydrocarbon CH and the carbon monoxide CO of complete oxidation of by-product only, emits a large amount of heat simultaneously.The hydrocarbon CH of complete oxidation does not account for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.1%, carbon monoxide CO accounts for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.3%, because the conversion zone temperature is relatively low, so there is not oxynitrides to produce.Air measures than being made into according to chemical reaction with the premix gas of gasification petroleum hydrocarbon, beds was dark red state when petroleum hydrocarbon on catalyst complete oxidation took place, but there is not flame to produce, catalyst surface temperature equates everywhere, petroleum hydrocarbon under catalyst action during by complete oxidation catalyst surface temperature reduce by 210 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the normal pressure flame combustion.
Embodiment 4
A, the cerous nitrate that will wait molal quantity and two kinds of compounds of calcium nitrate are mixed with solution;
B, cerous nitrate and calcium nitrate solution be impregnated in unformed Al
2O
3-SiO
2On the carrier, after 55 ℃ of abundant dryings, it is put in slowly is warmed up to 250 ℃ in the muffle furnace, be incubated after 2 hours to cool off naturally and promptly get the carrier of handling with stove;
C, the manganese nitrate that will wait molal quantity and two kinds of compound wiring solution-formings of cobalt nitrate impregnated in the unformed Al that the b step process is crossed
2O
3-SiO
2On the carrier, fully dry in 55 ℃;
D, the unformed Al that the c step process is crossed
2O
3-SiO
2Carrier is put in the muffle furnace, heats up with 110 ℃/30 minutes speed, is incubated 2 hours after 700 ℃, cools off naturally with stove then, promptly gets catalyst.
Contain composition in the gained catalyst and be (quality percentage composition):
Al
2O
3-SiO
2Carrier 90.8%
Ceria 5.7%, calcium oxide 1.9%
Manganese dioxide 0.8%, cobalt sesquioxide 0.8%
Catalyst being applied as in wide component petroleum hydrocarbon C1～C10 complete oxidation: catalyst is heated to 480 ℃ in air, the premix gas of blowing air and gasification petroleum hydrocarbon on catalyst, catalytic oxidation takes place and generates carbon dioxide in petroleum hydrocarbon on catalyst, water, while is a small amount of not the hydrocarbon CH and the carbon monoxide CO of complete oxidation of by-product only, emits a large amount of heat simultaneously.The hydrocarbon CH of complete oxidation does not account for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.1%, carbon monoxide CO accounts for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.3%, because the conversion zone temperature is relatively low, so there is not oxynitrides to produce.Air measures than being made into according to chemical reaction with the premix gas of gasification petroleum hydrocarbon, beds was dark red state when petroleum hydrocarbon on catalyst complete oxidation took place, but there is not flame to produce, catalyst surface temperature equates everywhere, petroleum hydrocarbon under catalyst action during by complete oxidation catalyst surface temperature reduce by 230 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the normal pressure flame combustion.
Embodiment 5
A, the calcium nitrate that will wait molal quantity and two kinds of compounds of barium nitrate are mixed with solution;
B, calcium nitrate and barium nitrate be impregnated in unformed Al
2O
3-SiO
2On the carrier, after 55 ℃ of abundant dryings, it is put in slowly is warmed up to 260 ℃ in the muffle furnace, be incubated after 4 hours to cool off naturally and promptly get the carrier of handling with stove;
C, will wait the nitric acid of molal quantity to bore and two kinds of compound wiring solution-formings of nickel nitrate again, impregnated in the unformed Al that the b step process is crossed
2O
3-SiO
2On the carrier, fully dry in 55 ℃;
D, the unformed Al that the c step process is crossed
2O
3-SiO
2Carrier is put in the muffle furnace, heats up with 120 ℃/30 minutes speed, is incubated 4 hours after 550 ℃, cools off naturally with stove then, promptly gets catalyst.
Contain composition in the gained catalyst and be (quality percentage composition):
Al
2O
3-SiO
2Carrier 88.3%
Calcium oxide 2.6%, barium monoxide 7.3%
Nickel oxide 0.8%, cobalt sesquioxide 1.0%
Catalyst being applied as in wide component petroleum hydrocarbon C1～C10 complete oxidation: catalyst is heated to 490 ℃ in air, the premix gas of blowing air and gasification petroleum hydrocarbon on catalyst, catalytic oxidation takes place and generates carbon dioxide in petroleum hydrocarbon on catalyst, water, while is a small amount of not the hydrocarbon CH and the carbon monoxide CO of complete oxidation of by-product only, emits a large amount of heat simultaneously.The hydrocarbon CH of complete oxidation does not account for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.1%, carbon monoxide CO accounts for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.3%, because the conversion zone temperature is relatively low, so there is not oxynitrides to produce.Air measures than being made into according to chemical reaction with the premix gas of gasification petroleum hydrocarbon, beds was dark red state when petroleum hydrocarbon on catalyst complete oxidation took place, but there is not flame to produce, catalyst surface temperature equates everywhere, petroleum hydrocarbon under catalyst action during by complete oxidation catalyst surface temperature reduce by 230 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the normal pressure flame combustion.
Embodiment 6
A, the cerous nitrate that will wait molal quantity and two kinds of compounds of barium nitrate are mixed with solution;
B, with cerous nitrate and barium nitrate solution impregnation in unformed Al
2O
3-SiO
2On the carrier, after 60 ℃ of abundant dryings, it is put in slowly is warmed up to 300 ℃ in the muffle furnace, be incubated after 2 hours to cool off naturally and promptly get the carrier of handling with stove;
C, will wait manganese nitrate and two kinds of compound wiring solution-formings of nickel nitrate of molal quantity again, impregnated in the unformed Al that the b step process is crossed
2O
3-SiO
2On the carrier, fully dry in 60 ℃;
D, the unformed Al that the c step process is crossed
2O
3-SiO
2Carrier is put in the muffle furnace, heats up with 140 ℃/30 minutes speed, is incubated 2 hours after 500 ℃, cools off naturally with stove then, promptly gets catalyst.
Contain composition in the gained catalyst and be (quality percentage composition):
Al
2O
3-SiO
2Carrier 92.8%
Ceria 2.7%, barium monoxide 2.5%
Manganese dioxide 1.1%, nickel oxide 0.9%
Catalyst being applied as in wide component petroleum hydrocarbon C1～C10 complete oxidation: catalyst is heated to 500 ℃ in air, the premix gas of blowing air and gasification petroleum hydrocarbon on catalyst, catalytic oxidation takes place and generates carbon dioxide in petroleum hydrocarbon on catalyst, water, while is a small amount of not the hydrocarbon CH and the carbon monoxide CO of complete oxidation of by-product only, emits a large amount of heat simultaneously.The hydrocarbon CH of complete oxidation does not account for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.1%, carbon monoxide CO accounts for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.3%, because the conversion zone temperature is relatively low, so there is not oxynitrides to produce.Air measures than being made into according to chemical reaction with the premix gas of gasification petroleum hydrocarbon, beds was dark red state when petroleum hydrocarbon on catalyst complete oxidation took place, but there is not flame to produce, catalyst surface temperature equates everywhere, petroleum hydrocarbon under catalyst action during by complete oxidation catalyst surface temperature reduce by 250 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the normal pressure flame combustion.
Embodiment 7
A, the cerous nitrate that will wait molal quantity and two kinds of compounds of barium nitrate are mixed with solution;
B, with cerous nitrate and barium nitrate solution impregnation in unformed Al
2O
3-SiO
2On the carrier, after 57 ℃ of abundant dryings, it is put in slowly is warmed up to 280 ℃ in the muffle furnace, be incubated after 2.5 hours to cool off naturally and promptly get the carrier of handling with stove;
C, will wait nickel nitrate and two kinds of compound wiring solution-formings of copper nitrate of molal quantity again, impregnated in the unformed Al that the b step process is crossed
2O
3-SiO
2On the carrier, fully dry in 57 ℃;
D, the unformed Al that the c step process is crossed
2O
3-SiO
2Carrier is put in the muffle furnace, heats up with 145 ℃/30 minutes speed, is incubated 5 hours after 800 ℃, cools off naturally with stove then, promptly gets catalyst.
Contain composition in the gained catalyst and be (quality percentage composition):
Al
2O
3-SiO
2Carrier 94.6%
Ceria 1.8%, barium monoxide 1.7%
Nickel oxide 0.9%, cupric oxide 1.0%
Catalyst being applied as in wide component petroleum hydrocarbon C1～C10 complete oxidation: catalyst is heated to 450 ℃ in air, the premix gas of blowing air and gasification petroleum hydrocarbon on catalyst, catalytic oxidation takes place and generates carbon dioxide in petroleum hydrocarbon on catalyst, water, while is a small amount of not the hydrocarbon CH and the carbon monoxide CO of complete oxidation of by-product only, emits a large amount of heat simultaneously.The hydrocarbon CH of complete oxidation does not account for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.1%, carbon monoxide CO accounts for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.3%, because the conversion zone temperature is relatively low, so there is not oxynitrides to produce.Air measures than being made into according to chemical reaction with the premix gas of gasification petroleum hydrocarbon, beds was dark red state when petroleum hydrocarbon on catalyst complete oxidation took place, but there is not flame to produce, catalyst surface temperature equates everywhere, petroleum hydrocarbon under catalyst action during by complete oxidation catalyst surface temperature reduce by 250 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the normal pressure flame combustion.
Embodiment 8
A, the calcium nitrate that will wait molal quantity and barium nitrate are mixed with solution for two kinds;
B, with calcium nitrate and barium nitrate solution impregnation in unformed Al
2O
3-SiO
2On the carrier, after 60 ℃ of abundant dryings, it is put in slowly is warmed up to 230 ℃ in the muffle furnace, be incubated after 2 hours to cool off naturally and promptly get the carrier of handling with stove;
C, will wait manganese nitrate and two kinds of compound wiring solution-formings of copper nitrate of molal quantity again, impregnated in the unformed Al that the b step process is crossed
2O
3-SiO
2On the carrier, fully dry in 57 ℃;
D, the unformed Al that the c step process is crossed
2O
3-SiO
2Carrier is put in the muffle furnace, heats up with 145 ℃/30 minutes speed, is incubated 4 hours after 680 ℃, cools off naturally with stove then, promptly gets catalyst.
Contain composition in the gained catalyst and be (quality percentage composition):
Al
2O
3-SiO
2Carrier 91.5%
Calcium oxide 1.8%, barium monoxide 5.0%
Manganese dioxide 0.9%, cupric oxide 0.8%
Catalyst being applied as in wide component petroleum hydrocarbon C1～C10 complete oxidation: catalyst is heated to 480 ℃ in air, the premix gas of blowing air and gasification petroleum hydrocarbon on catalyst, catalytic oxidation takes place and generates carbon dioxide in petroleum hydrocarbon on catalyst, water, while is a small amount of not the hydrocarbon CH and the carbon monoxide CO of complete oxidation of by-product only, emits a large amount of heat simultaneously.The hydrocarbon CH of complete oxidation does not account for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.1%, carbon monoxide CO accounts for the quality percentage composition of all combustion products that petroleum hydrocarbon oxidizing generates less than 0.3%, because the conversion zone temperature is relatively low, so there is not oxynitrides to produce.Air measures than being made into according to chemical reaction with the premix gas of gasification petroleum hydrocarbon, beds was dark red state when petroleum hydrocarbon on catalyst complete oxidation took place, but there is not flame to produce, catalyst surface temperature equates everywhere, petroleum hydrocarbon under catalyst action during by complete oxidation catalyst surface temperature reduce by 250 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the normal pressure flame combustion.
Claims (3)
1, a kind of catalyst that is used for wide component petroleum hydrocarbon C1-C10 complete oxidation, it is characterized in that this catalyst with choose any one kind of them in cerous nitrate, calcium nitrate, three kinds of compounds of barium nitrate or two kinds be mixed with solution impregnation in unformed Al
2O
3-SiO
2On the carrier, molal quantity equates when selecting two kinds of compounds for use, after 50-100 ℃ of abundant drying, is positioned over and slowly is warmed up to 200-300 ℃ in the muffle furnace, is incubated 2-6 hour, promptly gets the carrier of handling after the cooling naturally; Again any one or two kinds in manganese nitrate, cobalt nitrate, nickel nitrate, four kinds of compounds of copper nitrate are mixed with solution impregnation on the carrier of handling, molal quantity equates when selecting two kinds of compounds for use, fully dry in 50～60 ℃, the speed that is positioned in the muffle furnace with 100～150 ℃/30 minutes heats up, after 400-800 ℃, be incubated 1-4 hour, promptly get catalyst after the cooling naturally; The quality percentage composition of each component in the gained catalyst: unformed Al
2O
3-SiO
2Carrier 85-95%, any one content or two kinds total content 0.9-2.1% in manganese oxide, cobalt oxide, nickel oxide, four kinds of compounds of cupric oxide; Any one content or two kinds total content 4.1-12.9% in cerium oxide, calcium oxide, three kinds of compounds of barium monoxide.
2, Preparation of catalysts method according to claim 1 is characterized in that following these steps to carrying out:
A, with choose any one kind of them in cerous nitrate, calcium nitrate, the barium nitrate or two kinds be mixed with solution, molal quantity equates when selecting two kinds of compounds for use;
B, with described solution impregnation in unformed Al
2O
3-SiO
2On the carrier, after 50-100 ℃ of abundant drying, it is put in slowly is warmed up to 200-300 ℃ in the muffle furnace, be incubated after 2-6 hour to cool off naturally and promptly get the carrier of handling with stove;
C, with choose any one kind of them in manganese nitrate, cobalt nitrate, nickel nitrate, the copper nitrate or two kinds be mixed with solution, impregnated in the unformed Al that the b step process is crossed
2O
3-SiO
2On the carrier, in 50～60 ℃ of abundant dryings, molal quantity equates when wherein selecting two kinds of compounds for use;
D, the unformed Al that the c step process is crossed
2O
3-SiO
2Carrier is put in the muffle furnace, heats up with 100～150 ℃/30 minutes speed, is incubated 1-4 hour after 400-800 ℃, cools off naturally with stove then, promptly gets catalyst.
3, according to the described Application of Catalyst of claim 1: catalyst is heated to 450～500 ℃ in air, the premix gas of blowing air and gasification wide cut petroleum hydrocarbon C1-C10 on catalyst, complete oxidation takes place and generates carbon dioxide and water in wide cut petroleum hydrocarbon C1-C10 on catalyst, its surface temperature reduces by 200～250 ℃ than the flame temperature of equivalent petroleum hydrocarbon when the flame combustion, catalytic bed is kermesinus, does not have flame to produce.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100522021A CN1322920C (en) | 2005-01-28 | 2005-01-28 | Petroleum hydrocarbon completely catalyzed oxidative catalyst |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100522021A CN1322920C (en) | 2005-01-28 | 2005-01-28 | Petroleum hydrocarbon completely catalyzed oxidative catalyst |
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| CN1322920C true CN1322920C (en) | 2007-06-27 |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01270943A (en) * | 1988-04-21 | 1989-10-30 | Matsushita Electric Ind Co Ltd | Perovskite oxidation catalyst |
| CN1060793A (en) * | 1990-10-22 | 1992-05-06 | 华东化工学院 | Multieffective non-noble metal catalyst |
| CN1210475A (en) * | 1996-02-12 | 1999-03-10 | 国家研究院 | Catalysts for full oxidation of volatile organic compounds |
| CN1275427A (en) * | 2000-06-09 | 2000-12-06 | 厦门大学 | Complete oxidation catalyst for low concentration C1/C2 organic effluents |
| CN1346704A (en) * | 2000-10-11 | 2002-05-01 | 舒德化学公司 | Oxidation catalyst |
| US20030162847A1 (en) * | 2002-02-26 | 2003-08-28 | Harford Steven Thomas | Apparatus for producing high molecular weight liquid hydrocarbons from methane and/or natural gas |
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2005
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01270943A (en) * | 1988-04-21 | 1989-10-30 | Matsushita Electric Ind Co Ltd | Perovskite oxidation catalyst |
| CN1060793A (en) * | 1990-10-22 | 1992-05-06 | 华东化工学院 | Multieffective non-noble metal catalyst |
| CN1210475A (en) * | 1996-02-12 | 1999-03-10 | 国家研究院 | Catalysts for full oxidation of volatile organic compounds |
| CN1275427A (en) * | 2000-06-09 | 2000-12-06 | 厦门大学 | Complete oxidation catalyst for low concentration C1/C2 organic effluents |
| CN1346704A (en) * | 2000-10-11 | 2002-05-01 | 舒德化学公司 | Oxidation catalyst |
| US20030162847A1 (en) * | 2002-02-26 | 2003-08-28 | Harford Steven Thomas | Apparatus for producing high molecular weight liquid hydrocarbons from methane and/or natural gas |
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| CN1654119A (en) | 2005-08-17 |
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