CN116237064A - Non-methane total hydrocarbon purifying catalyst composition, catalyst, preparation method and application - Google Patents
Non-methane total hydrocarbon purifying catalyst composition, catalyst, preparation method and application Download PDFInfo
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Abstract
The invention provides a non-methane total hydrocarbon purification catalyst composition, a catalyst, a preparation method and application thereof. The non-methane total hydrocarbon clean-up catalyst composition comprises: a first component: soluble ferrous sulfate, or a mixture of soluble ferrous sulfate and soluble manganese sulfate; and a second component: alkaline earth metal hydroxides; wherein the alkaline earth metal hydroxide is Ba (OH) 2 And/or Sr (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the And a third component: a manganese source compound. In the present invention, ba (OH) is used as the alkaline earth metal hydroxide 2 And/or Sr (OH) 2 The sulfate corresponding to the two materials is water insoluble and can not be dissolved by the coke oven smoke, and the sulfate is used as a carrier to disperse active componentsFe and Mn added later have the functions of water resistance and sulfur thinning, so that the tolerance of the catalyst is improved.
Description
Technical Field
The invention relates to the fields of chemical industry, energy sources, environmental protection and the like, in particular to a non-methane total hydrocarbon purification catalyst composition, a catalyst, a preparation method and application thereof.
Background
In the coking process of coal, the emission of non-methane total hydrocarbon can be generated due to leakage, incomplete combustion, furnace wall leakage and other reasons, and the environment is seriously polluted. On the one hand, it is the main precursor of atmospheric fine particulate matter (PM 2.5), PM2.5 being the main cause of urban haze pollution; on the other hand, under illumination, non-methane total hydrocarbons are easy to react with nitrogen oxides, so that ozone pollution or photochemical smog is generated, and ecological environment and human health are endangered.
In carrying out the present invention, applicants have found that conventional non-methane total hydrocarbon clean-up catalysts have a relatively short life and relatively high cost due to sulfur intolerance.
Disclosure of Invention
First, the technical problem to be solved
In view of this, the present invention is expected to solve at least one of the technical problems.
(II) technical scheme
To achieve the above object, according to a first aspect of the present invention, there is provided a non-methane total hydrocarbon purification catalyst composition. The non-methane total hydrocarbon clean-up catalyst composition comprises:
a first component: soluble ferrous sulfate, or a mixture of soluble ferrous sulfate and soluble manganese sulfate;
and a second component: alkaline earth metal hydroxides; wherein the alkaline earth metal hydroxide is Ba (OH) 2 And/or Sr (OH) 2 ；
And a third component: a manganese source compound;
wherein the molar ratio of the first component to the second component is in the range of 1:0.6-1:1; the molar ratio of the first component to the third component is in the range of 1:0.27 to 1:0.40.
In some embodiments of the invention, the manganese source compound is KMnO 4 、K 2 MnO 4 、NaMnO 4 And/or Na 2 MnO 4 ；
In some embodiments of the invention, the soluble ferrous sulfate is FeSO 4 ·7H 2 O、FeSO 4 ·6H 2 O and/or FeSO 4 ·5H 2 O。
In some embodiments of the invention, the soluble manganese sulfate is MnSO 4 ·4H 2 O and/or MnSO 4 ·H 2 O; wherein, in the mixture of the soluble ferrous sulfate and the soluble manganese sulfate, the mole percentage of the soluble manganese sulfate is between 5 percent and 50 percent.
In some embodiments of the invention, the first component is FeSO 4 ·7H 2 O; the second component is Ba (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein FeSO 4 ·7H 2 O、Ba(OH) 2 、KMnO 4 The molar ratio of (1) (0.4-1.2) to (0.1-0.6).
In some embodiments of the invention, further comprising: and a fourth component: titanium sol or silica sol.
In order to achieve the above object, according to a second aspect of the present invention, there is also provided a method for producing a non-methane total hydrocarbon purification catalyst. The preparation method of the non-methane total hydrocarbon purification catalyst comprises the following steps:
step A, carrying out solid-solid mixing grinding on a first component and a second component; wherein the first component is soluble ferrous sulfate or a mixture of soluble ferrous sulfate and soluble manganese sulfate; wherein the second component is alkaline earth metal hydroxide, and the alkaline earth metal hydroxide is Ba (OH) 2 And/or Sr (OH) 2 ；
B, adding a third component into the material obtained in the step A for solid-solid mixing grinding; wherein the third component is a manganese source compound;
step D, adding a binder and a pore-forming agent into the material obtained in the step B, and mixing, grinding, forming and drying to obtain a semi-finished catalyst;
and F, roasting the semi-finished catalyst to obtain the non-methane total hydrocarbon purifying catalyst.
In some embodiments of the present invention, between step D and step F, further comprises: step E, immersing the semi-finished catalyst into titanium sol or silica sol; wherein if immersed in the titanium sol, the titanium sol attached to the semi-finished catalyst is calcined to form TiO on the surface of the non-methane total hydrocarbon purifying catalyst 2 A shell layer; if immersed in the silica sol, the silica sol attached to the semi-finished catalyst is calcined to form SiO on the surface of the non-methane total hydrocarbon purification catalyst 2 A shell layer.
In some embodiments of the invention, step E comprises: immersing the semi-finished catalyst in titanium sol, and TiO in the titanium sol 2 The mass concentration of (2) is 0.02-2%.
In some embodiments of the invention, in step A, the first component is FeSO 4 ·7H 2 O, the second component is Ba (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The solid-solid mixing grinding time is between 30 and 60 minutes.
In some embodiments of the invention, in step B, the manganese source compound is KMnO 4 The solid-solid mixing grinding time is between 20 and 60 minutes.
In some embodiments of the present invention, between step B and step D further comprises: step C, washing and drying the material obtained in the step B to obtain a washed material; wherein, the drying is: drying at 100-120 deg.c for 1-10 hr or natural air drying for 12-24 hr; the step D of adding the binder and the pore-forming agent into the material obtained in the step B comprises the following steps: and C, adding a binder and a pore-forming agent into the water-washed material obtained in the step C.
In some embodiments of the invention, in step D, the binder comprises: an inorganic binder and an organic binder, wherein the inorganic binder is selected from one or more of the following materials: titanium sol, silica sol and aluminum sol, wherein the mass percentage of the titanium sol, the silica sol and the aluminum sol in the total amount of the materials after the inorganic binder is added is between 10% and 30%; the organic binder is selected from one or more of the following materials: carboxymethyl cellulose and sesbania gum; the mass percentage of the organic binder is between 0.01 and 0.4 percent of the total material after the organic binder is added.
In some embodiments of the invention, in step D, the pore-forming agent is selected from one or more of the following materials: starch, flour; the mass percentage of the material accounting for the total amount of the added pore-forming agent is between 0.1 percent and 5 percent.
In some embodiments of the present invention, in the step D, the mixing and grinding time is 20-60 min; drying: drying at 120deg.C for 2-24 hr.
In some embodiments of the invention, in step F, the firing is: roasting at 350-700 deg.c for 1-4 hr.
To achieve the above object, according to a third aspect of the present invention, there is provided a non-methane total hydrocarbon purification catalyst. The non-methane total hydrocarbon purifying catalyst is prepared by the preparation method, and is granular or honeycomb.
In order to achieve the above object, according to a fourth aspect of the present invention, there is also provided the use of the above non-methane total hydrocarbon purification catalyst composition for removing non-methane total hydrocarbons from coke oven flue gas or the use of the above non-methane total hydrocarbon purification catalyst for removing non-methane total hydrocarbons from coke oven flue gas.
(III) beneficial effects
As can be seen from the technical scheme, the invention has at least one of the following advantages:
(1) The applicant has found through experiments and scientific analysis that: in the case of non-noble metal catalysts, which are susceptible to deactivation by sulfur and water due to their nature, the primary reason for sulfur deactivation is that sulfur reacts with the active component to sulfate the active component, and the presence of water further exacerbates the sulfation of the active component.
In the present invention, ba (OH) is used as the alkaline earth metal hydroxide 2 And/or Sr (OH) 2 The sulfate corresponding to the two materials is water-insoluble and can not be dissolved by the coke oven flue gas, and the sulfate is used as a carrier to disperse the active component Fe and Mn added later, so that the sulfate has the functions of water resistance and sulfur removal, and the tolerance of the catalyst is further improved.
(2) In the invention, feSO is adopted 4 ·7H 2 O、FeSO 4 ·6H 2 O and/or FeSO 4 ·5H 2 O as a main component of the first component.
First, fe is chosen as the main element of the catalyst, mainly because iron oxide is a non-toxic catalyst and is superior to relatively inexpensive metal oxides such as Cu, mn, co, etc. in terms of sulfur resistance. In addition, the iron compound is low in cost, can be added in a large amount, and does not affect the overall catalytic effect even if some of the iron compound is deactivated by sulfur.
Secondly, experiments prove that more than 5 crystal waters must be contained in the soluble ferrous sulfate, otherwise, the poor solubility can affect the performance of the prepared catalyst. In particular, by FeSO 4 ·H 2 O is used as a catalyst prepared by soluble ferrous sulfate raw materials, and the catalytic performance and the use of FeSO 4 ·7H 2 The performance of the O catalyst is reduced by about 90 percent; the catalyst prepared by taking ferric sulfate as a raw material has no catalytic effect at all. In addition, since the stability of ferrous sulfate containing 5 or less crystal waters is poor, the performance of the prepared catalyst is also unstable.
Finally, the catalytic activity and sulfur resistance can be balanced by partially replacing the soluble ferrous sulfate in the first component with soluble manganese sulfate.
(3) The manganese source compound adopts potassium permanganate. On the one hand, manganese and iron form a synergistic effect, and the catalytic activity is further improved. On the other hand, amorphous ferric hydroxide with smaller crystal grains can be obtained by rapid oxidation of potassium permanganate, and nano ferric oxide can be obtained by controlling the roasting temperature and the roasting time. Smaller grain sizes have larger specific surface areas and more lattice defects, and can provide more active sites.
(4) In the preparation method, feSO is firstly carried out 4 ·7H 2 O、Ba(OH) 2 Carrying out solid-solid mixing grinding; then adding KMnO 4 Solid-solid mixing milling is performed so that the first component is able to sufficiently react with the second component as a first step:
FeSO 4 ·7H 2 O+Ba(OH) 2 →BaSO 4 +Fe(OH) 2 +7H 2 O…………①
the reactants of the reaction are reacted with a manganese source compound in the following second step:
KMnO 4 +3Fe(OH) 2 →MnO 2 +3FeOOH+KOH+H 2 O…………②
and the first component remaining in the first reaction step reacts with the manganese source compound as follows:
10KMnO 4 +30FeSO 4 ·7H 2 O→10MnO 2 +30FeOOH+5K 2 SO 4 +25H 2 SO 4 +170H 2 O ③
by the above arrangement, the controllability of the reaction process and the purity of the produced substances are ensured.
(5) Coating a layer of TiO on the surface of the catalyst 2 Shell layer, tiO 2 Has high sulfur resistance and high water resistance, SO that 2 Is not easy to adsorb on the surface of the catalyst, thereby preventing the sulfation of the active components and protecting the active components. But TiO 2 The shell layer must not be too thick to prevent diffusion of non-methane total hydrocarbons and oxygen to the active site.
Drawings
FIG. 1 is a flow chart of a method for preparing a non-methane total hydrocarbon clean-up catalyst according to the present invention.
Detailed Description
The applicant has found through experiments and scientific analysis that: in the case of non-noble metal catalysts, which are susceptible to deactivation by sulfur and water due to their nature, the primary reason for sulfur deactivation is to react with the active component and to sulfate the active component, the presence of water further exacerbates the sulfation of the active component.
Based on the research results, the invention selects Fe as the main element of the catalyst, adds the active component sacrificial agent, takes in-situ generated water-insoluble alkali metal sulfate as the carrier, and covers TiO on the surface of the catalyst 2 Shell layer and other means to achieve SO reduction 2 Adsorption on the catalyst surface, increasing the SO-resistance of the catalyst 2 Tolerance purposes.
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
According to a first aspect of the present invention there is provided a non-methane total hydrocarbon clean-up catalyst composition. The non-methane total hydrocarbon clean-up catalyst composition comprises:
a first component: soluble ferrous sulfate, or a mixture of soluble ferrous sulfate and soluble manganese sulfate;
and a second component: an alkaline earth metal hydroxide, said alkaline earth metal hydroxide being Ba (OH) 2 And/or Sr (OH) 2 ；
And a third component: a manganese source compound;
wherein the molar ratio of the first component to the second component is in the range of 1:0.6-1:1; the molar ratio of the first component to the third component is in the range of 1:0.27 to 1:0.40.
For the first component of the composition, the soluble ferrous sulfate is FeSO 4 ·7H 2 O、FeSO 4 ·6H 2 O and/or FeSO 4 ·5H 2 O, soluble manganese sulfate is MnSO 4 ·H 2 O and/or MnSO 4 ·4H 2 O. And if the first component is a mixture of soluble ferrous sulfate and soluble manganese sulfate, the soluble manganese sulfate accounts for 5-50 mole percent of the whole mixture.
First, fe is chosen as the main element of the catalyst, mainly because iron oxide is a non-toxic catalyst and compared to relatively inexpensive metal oxides such as Cu, mn, co, etc. for sulfur resistance. In addition, the iron compound is extremely low in price and can be added in a large amount, and even if part of the iron compound is deactivated by sulfur, the whole catalytic effect is not affected.
Secondly, experiments prove that more than 5 crystal waters must be contained in the soluble ferrous sulfate, otherwise, the poor solubility can affect the performance of the prepared catalyst. In particular, it has been found experimentally that from FeSO 4 ·H 2 O is used as a catalyst prepared by soluble ferrous sulfate raw materials, and the catalytic performance and the use of FeSO 4 ·7H 2 Compared with the catalyst prepared by O, the performance of the catalyst is reduced by 90 percent; the catalyst prepared by taking ferric sulfate as a raw material has no catalytic effect at all.In addition, since the stability of ferrous sulfate containing 5 or less crystal waters is poor, the performance of the prepared catalyst is also unstable.
Finally, the catalytic activity and sulfur resistance can be balanced by partially replacing the soluble ferrous sulfate in the first component with soluble manganese sulfate.
In the invention, the manganese source compound is KMnO 4 、K 2 MnO 4 、NaMnO 4 And/or Na 2 MnO 4 。
For manganese source compounds in the composition, KMnO is the specific example 4 . On the one hand, manganese and iron form a synergistic effect, and the catalytic activity is further improved. On the other hand, amorphous ferric oxide hydroxide with smaller crystal grains can be obtained through rapid oxidation of potassium permanganate, and the nano ferric oxide can be obtained by controlling the roasting temperature and the roasting time. Smaller grain sizes have larger specific surface areas and more lattice defects, and can provide more active sites.
In a preferred embodiment of the invention, the composition further comprises a titanium sol which forms TiO on the catalyst surface 2 A shell layer; or silica sol, which forms SiO on the catalyst surface 2 A shell layer. With TiO 2 The shell layer is exemplified by covering a layer of TiO on the surface of the catalyst 2 Shell layer, tiO 2 Has high sulfur resistance and high water resistance, SO that 2 Is not easy to be adsorbed on the surface of the catalyst, thereby preventing the sulfation of the active components and protecting the active components. But TiO 2 The shell layer must not be too thick to prevent diffusion of non-methane total hydrocarbons and oxygen to the active site. The principle and function of silica sol are similar to those of silica sol, and will not be described again.
In a preferred embodiment of the invention, the first component is FeSO 4 ·7H 2 O; the second component is Ba (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The third component is KMnO 4 The method comprises the steps of carrying out a first treatment on the surface of the The fourth component is titanium sol. Wherein FeSO 4 ·7H 2 O、Ba(OH) 2 、KMnO 4 The molar ratio of (1) (0.4-1.2) to (0.1-0.6). Namely by FeSO 4 ·7H 2 The mole number of O is 1 part based on the mole number of Ba (OH) 2 0.4 to 1.2 parts of KMnO 4 0.1 to 0.6 part. In such a ratioThe composition has optimal properties.
According to a second aspect of the present invention, there is also provided a method for producing a non-methane total hydrocarbon purification catalyst using the above non-methane total hydrocarbon purification catalyst composition. For details of the non-methane total hydrocarbon clean-up catalyst composition, reference is made to the above-related description and will not be repeated here.
FIG. 1 is a flow chart of a method for preparing a non-methane total hydrocarbon clean-up catalyst according to the present invention. As shown in fig. 1, the preparation method of the non-methane total hydrocarbon purification catalyst in the invention comprises the following steps:
step A, carrying out solid-solid mixing grinding on a first component and a second component;
wherein the first component is soluble ferrous sulfate or a mixture of soluble ferrous sulfate and soluble manganese sulfate; wherein the second component is an alkaline earth metal hydroxide, and the alkaline earth metal hydroxide is Ba (OH) 2 And/or Sr (OH) 2 。
FeSO 4 ·7H 2 The ratio of O to alkaline earth metal hydroxide is 1:0.6-1:1, preferably 1:0.8-1:0.85, and the main purpose is to fully react the alkaline earth metal hydroxide, avoid residue (as shown in formula (1)), and increase FeSO 4 ·7H 2 O to neutralize KMnO 4 And (3) alkalinity after the reaction.
FeSO 4 ·7H 2 O+Ba(OH) 2 →BaSO 4 +Fe(OH) 2 +7H 2 O……………①
The alkaline earth hydroxide is barium hydroxide and/or strontium hydroxide, and other alkaline earth metal or alkali metal hydroxides are not used because other alkaline earth metal or alkali metal sulfates have certain water solubility and the coke oven fume contains high content of water. Alkaline earth metal sulphates produced, e.g. BaSO 4 As a carrier, the active component Fe and Mn added later are dispersed, and the sulfur resistance of the catalyst is improved.
The solid-solid mixing and grinding process adopts a mixing mill or a kneader for 20-60 min, preferably 20-40 min. Compared with the solution reaction, the solid-solid reaction is slow, the mixing and grinding time is prolonged, which is favorable for full reaction, butToo long mixing and grinding time, fe 2+ The product obtained by slow oxidation has larger crystal grains and is unfavorable for catalysis, so that the solid-solid mixing grinding time cannot be excessively long.
Step B, adding a third component into the material obtained in the step A for solid-solid mixing grinding;
preferably, the third component is a manganese source compound.
Specifically, for step B, KMnO is used 4 As a manganese source, forms a synergistic effect with Fe to improve the catalytic performance, and in addition, as a strong oxidant, rapidly oxidizes Fe 2+ The formed product has smaller crystal grain and better activity. FeSO 4 ·7H 2 O and KMnO 4 The molar ratio is 1:0.27-1:0.40, preferably 1:0.30-1:0.37.
The reaction can be disassembled into KMnO 4 Oxidation of Fe (OH) 2 (as in formula (2)), and KMnO 4 Excess FeSO in the oxidation system 4 ·7H 2 O (as in formula (3)) reacts in two ways. If KOH generated in the reaction of the formula (2) is not neutralized by acid, the reaction is not completely carried out, and the product contains potassium manganate, so that FeSO is reacted in the step A 4 ·7H 2 The excess O is to neutralize the KOH formed.
KMnO 4 +3Fe(OH) 2 →MnO 2 +3FeOOH+KOH+H 2 O………………②
10KMnO 4 +30FeSO 4 ·7H 2 O→10MnO 2 +30FeOOH+5K 2 SO 4 +25H 2 SO 4 +170H 2 ③
Formula (2) ×50+ formula (3), to obtain formula (4):
60KMnO 4 +150Fe(OH) 2 +30FeSO 4 ·7H 2 O→60MnO 2 +180FeOOH+30K 2 SO 4 +270H 2 O.....④
the common divisor 30 is reduced in the formula (4), and the formula (5) is obtained
2KMnO 4 +5Fe(OH) 2 +FeSO 4 ·7H 2 O→2MnO 2 +6FeOOH+K 2 SO 4 +9H 2 O…⑤
Therefore, ba (OH) 2 As alkaline earthFor the example of metal hydroxide, the molar ratios of the reactants are:
FeSO 4 ·7H 2 O/Ba(OH) 2 /KMnO 4 ＝6/5/2
so if FeSO is used 4 ·7H 2 The molar amount of O is 1, and the optimal Ba (OH) 2 The molar weight is 0.83, the best KMnO 4 The molar amount was 0.33.
Step C, washing and drying the material obtained in the step B to obtain a washed material;
for step C, the main purpose of this step is to wash off the K formed 2 SO 4 Not washing with water, but due to K 2 SO 4 In use, water in the atmosphere is absorbed, and part of active sites are covered, so that the activity of the catalyst is affected to a certain extent. In addition, the drying is to remove a part of water, otherwise the material is too wet to be extruded.
Step D, adding a binder and a pore-forming agent into the washed material, mixing, grinding, forming and drying to obtain a semi-finished catalyst;
for step D, the inorganic binder forms a metal oxide framework after calcination, mainly providing the final shaped catalyst strength. The inorganic binder is one or two or more of titanium sol, silica sol and aluminum sol, and is prepared from TiO 2 、SiO 2 、Al 2 O 3 Counting, and the addition amount is converted to 10-30% of the mass content. For example: a is the mass of the material, B is TiO 2 、SiO 2 、Al 2 O 3 The amount of gum to be counted is then B/(A+B) 100% should be equal to 10% to 30%, preferably 15% to 25%.
The organic binder has very little addition, good viscosity and good lubrication effect, mainly facilitates extrusion molding, provides the strength of a semi-finished product, and has the function of forming holes due to total or partial loss after roasting. The organic binder is one or two of carboxymethyl cellulose and sesbania gum, and the addition amount is converted into 0.01-0.4% of the mass content based on dry basis. For example: a is the mass of the material, B is the gum mass calculated on a dry basis, and then B/(A+B) 100% should be equal to 0.01-0.4%, preferably 0.05% -0.2%.
The pore-forming agent becomes CO after roasting 2 And H 2 O runs off to form cavities, which mainly serves to increase the pore volume and specific surface area of the final shaped catalyst, but the strength is lowered by excessive addition. The pore-forming agent is one or two of starch and flour, and the addition amount is converted to 0.1-5% of the mass content, preferably 0.5-1.5%.
Drying is required after extrusion to remove free water, and the drying time is determined by the drying efficiency. The extrusion molding may be honeycomb, bar-shaped, or the like, and is not limited thereto.
Step E, immersing the semi-finished catalyst into titanium sol;
wherein the titanium sol attached to the semi-finished catalyst is dried and roasted to form TiO 2 A shell layer of TiO in the titanium sol 2 The mass concentration of (2) is 0.02-2%.
Alternatively, the titanium sol as above may be replaced by a silica sol, in which case the silica sol is dried and calcined to form SiO 2 A shell layer.
For the step E, the dried semi-finished catalyst is impregnated with titanium sol to cover TiO on the surface of the catalyst after roasting 2 Shell layer, tiO 2 Has high sulfur resistance and high water resistance, SO that 2 Is not easy to be adsorbed on the surface of the catalyst, thereby preventing the sulfation of the active components and protecting the active components. But TiO 2 The shell layer must not be too thick to prevent diffusion of non-methane total hydrocarbons and oxygen to the active site. It is difficult to measure the thickness of the shell layer to impregnate TiO in the liquid 2 Concentration limitations. TiO in the impregnating solution 2 The mass concentration is 0.02% -2%, preferably 0.05% -1%. A further drying is required after impregnation.
And F, roasting the semi-finished catalyst to obtain a finished product of the non-methane total hydrocarbon purification catalyst.
In a preferred embodiment of the present invention, the above method for preparing a non-methane total hydrocarbon purification catalyst specifically comprises:
step A, feSO 4 ·7H 2 Carrying out solid-solid mixing grinding on O and alkaline earth metal hydroxide for 30-60 min;
step B, adding KMnO into the materials obtained by mixing and grinding 4 Mixing and grinding for 20-60 min;
step C, washing the materials obtained by mixing and grinding with water to remove the soluble salt K 2 SO 4 Drying at 100-120 deg.c for 1-10 hr or natural air drying for 12-24 hr;
step D, adding an inorganic binder, an organic binder and a pore-forming agent into the material after washing, and mixing and grinding for 20-60 min; then extrusion molding is carried out, and drying is carried out for 2-24 hours at 120 ℃;
step E, dipping the formed and dried catalyst into titanium sol, attaching a layer of titanium sol on the surface, and then drying at 120 ℃ for 2-10 hr;
and F, roasting at 350-700 ℃ for 1-4 hr to obtain the catalyst finished product.
Wherein, the roasting temperature is preferably 350-550 ℃.
According to a third aspect of the present invention there is also provided a non-methane total hydrocarbon clean-up catalyst. The non-methane total hydrocarbon purifying catalyst is prepared by adopting the preparation method, and is granular or honeycomb.
According to a fourth aspect of the present invention there is also provided the use of a non-methane total hydrocarbon purification catalyst composition as described above, or a non-methane total hydrocarbon purification catalyst as described above, for the removal of non-methane total hydrocarbons from coke oven flue gas.
The present invention will be described in detail with reference to specific examples.
Comparative example 1
Step A', feSO is carried out 4 ·7H 2 O and Ca (OH) 2 Carrying out solid-solid mixing grinding for 20min;
step B', adding KMnO into the obtained material 4 Then carrying out solid-solid mixing grinding for 15min; wherein, the mol ratio of each reactant is as follows: feSO 4 ·7H 2 O/Ca(OH) 2 /KMnO 4 ＝2/5/6；
Step C', adding the obtained material into an inorganic binder, an organic binder and a pore-forming agent, and mixing and grinding for 15min; then extrusion molding, drying at 120deg.C for 2hr;
the test shows that the 10 percent conversion temperature (T10) of the propane is 280 ℃, and the 90 percent conversion temperature (T90) is 400 ℃; at T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.863%/h.
Example 1
Step A, feSO 4 ·7H 2 O and Ba (OH) 2 Carrying out solid-solid mixing grinding for 30min;
step B, adding KMnO into the obtained material 4 Then carrying out solid-solid mixing grinding for 20min; wherein, the mol ratio of each reactant is as follows: feSO 4 ·7H 2 O/Ba(OH) 2 /KMnO 4 ＝6/5/2；
Step C, washing the obtained material with water to remove the soluble salt K 2 SO 4 Drying at 100deg.C for 1hr;
step D, adding an inorganic binder into the material after washing: and an organic binder: pore-forming agent: mixing and grinding for 20min; then extrusion molding, drying at 120deg.C for 2hr;
step E, dipping the formed and dried catalyst into titanium sol, attaching a layer of titanium sol on the surface, and then drying for 2hr at 120 ℃; wherein, tiO in the impregnating solution 2 The mass concentration is 0.02%;
and F, roasting at 350 ℃ for 4 hours to obtain a catalyst finished product.
The test shows that the 10 percent conversion temperature (T10) of the propane is 150 ℃, and the 90 percent conversion temperature (T90) is 230 ℃; at T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.005%/h.
Example 2
This embodiment is similar to embodiment 1, except that: with FeSO at a molar percentage of 50% 4 ·7H 2 O and 50 mole percent MnSO 4 ·1H 2 O replaces FeSO in step A 4 ·7H 2 O。
The test shows that the 10 percent conversion temperature (T10) of the propane is 125 ℃, and the 90 percent conversion temperature (T90) is 210 ℃; at the position ofAt T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.020%/h.
Example 3
This embodiment is similar to embodiment 1, except that: by FeSO 4 ·5H 2 O replaces FeSO in step A 4 ·7H 2 O. The test shows that the 10 percent conversion temperature (T10) of the propane is 185 ℃ and the 90 percent conversion temperature (T90) is 270 ℃; at T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.009%/h.
Example 4
This embodiment is similar to embodiment 1, except that: with FeSO at a molar percentage of 75% 4 ·7H 2 O and 25 mol% MnSO 4 ·1H 2 O replaces FeSO in step A 4 ·7H 2 O。
The test shows that the 10 percent conversion temperature (T10) of the propane is 130 ℃, and the 90 percent conversion temperature (T90) is 225 ℃; at T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.012%/h.
Example 5
This embodiment is similar to embodiment 1, except that: using Sr (OH) 2 Instead of Ba (OH) in step A 2 。
The test shows that the 10 percent conversion temperature (T10) of the propane is 155 ℃ and the 90 percent conversion temperature (T90) is 240 ℃; at T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.007%/h.
Example 6
This embodiment is similar to embodiment 1, except that: adopts Na 2 MnO 4 Instead of KMnO in step B 4 。
The test shows that the 10 percent conversion temperature (T10) of the propane is 170 ℃, and the 90 percent conversion temperature (T90) is 265 ℃; at T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.016%/h.
Example 7
This example is similar to example 1, except thatIn the following steps: the molar ratio of each reactant is as follows: feSO 4 ·7H 2 O/Ba(OH) 2 /KMnO 4 ＝6/4/3。
The test shows that the 10 percent conversion temperature (T10) of the propane is 170 ℃ and the 90 percent conversion temperature (T90) is 280 ℃; at T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.015%/h.
Example 8
This embodiment is similar to embodiment 1, except that: step C' is omitted.
The test shows that the 10 percent conversion temperature (T10) of the propane is 200 ℃, and the 90 percent conversion temperature (T90) is 300 ℃; at T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.054%/h.
Example 9
This embodiment is similar to embodiment 1, except that: replacing the titanium sol in the step E' with a silica sol, wherein SiO in the silica sol 2 The mass concentration is 2%.
The test shows that the 10 percent conversion temperature (T10) of the propane is 240 ℃ and the 90 percent conversion temperature (T90) is 330 ℃; at T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.007%/h.
Example 10
This embodiment is similar to embodiment 1, except that:
in the step A, the solid-solid mixing grinding time is 60min;
in the step B, the solid-solid mixing grinding time is 60min;
in step C, naturally air-drying for 24hr;
in step D, the mixing and grinding time is 60min, and the drying time is 24hr;
in step E, the drying time is 10hr;
in step F, the mixture is baked at 700℃for 1hr.
The test shows that the 10 percent conversion temperature (T10) of the propane is 270 ℃ and the 90 percent conversion temperature (T90) is 385 ℃; at T90 temperature, 10% of water vapor and 10ppm of SO are introduced 2 The deactivation rate was 0.006%/h.
The 10% conversion temperature (T10), 90% conversion temperature (T90) and deactivation rate test methods for propane described in the above examples and comparative examples of the present invention were:
5g of catalyst is filled into a fixed bed reactor, gas containing 200ppm of propane, 8% of oxygen and the balance of nitrogen is introduced into the inlet of the reactor under normal pressure, slow temperature rise is carried out, the outlet propane concentration and the bed temperature are recorded, the conversion rate is calculated through the propane concentration, and the data of 10% conversion rate temperature (T10) and 90% conversion rate temperature (T90) of propane can be obtained. The bed layer is kept at a constant temperature to T90, 10 percent of water vapor and 10ppm of SO are introduced 2 And recording the concentration of the outlet propane in real time, calculating the conversion rate through the concentration of the propane, drawing a curve of the conversion rate of the propane and time, and performing primary fitting on the curve to obtain the inactivation rate. The conversion was calculated as follows:
thus, various embodiments of the present invention have been described in detail with reference to the accompanying drawings. The present invention should be clearly recognized by those skilled in the art in light of the above description.
Furthermore, the above definitions of the elements and methods are not limited to the specific structures, shapes or modes mentioned in the embodiments, and those of ordinary skill in the art can make simple modifications or substitutions thereof, for example:
(1) The water washing step of the step C can be omitted; or baking, washing with water, and drying at 120deg.C for 2-24 hr.
(2) The titanium sol in the step E can be replaced by silica sol, and the concentration range is unchanged.
In summary, the present invention provides a non-methane total hydrocarbon purification catalyst composition, catalyst, its preparation method and application, which is prepared by selecting Ba (OH) 2 And/or Sr (OH) 2 As a reactant, the corresponding active ingredient carrier can not lose efficacy due to dissolution in water, has the functions of water resistance and sulfur removal, and further improves the catalysisSulfur resistance of the catalyst. At the same time, feSO is adopted 4 ·7H 2 O as a reactant, can produce more stable active ingredients; by adopting potassium permanganate as a reactant, manganese can synergistically enhance the catalytic activity with iron on one hand, amorphous iron oxide with smaller crystal grains can be obtained on the other hand, and the nano iron oxide can be obtained by controlling the roasting temperature and the roasting time. Finally also through TiO 2 Or SiO 2 The shell layer improves the sulfur and water resistance of the catalyst. The non-methane total hydrocarbon purifying catalyst with excellent water resistance and sulfur resistance is obtained through the various means, and has good popularization and application prospects.
It should be noted that, for some implementations, if they are not critical to the present invention and are well known to those of ordinary skill in the art, they are not described in detail in the drawings or the specification, and may be understood with reference to the related art.
Further, the embodiments described above are provided solely for the purpose of enabling the present invention to meet the legal requirements and may be implemented in many different forms and should not be construed as limited to the embodiments set forth herein. Furthermore, the above definitions of the elements and methods are not limited to the specific structures, shapes or modes mentioned in the embodiments, and may be simply modified or replaced by those of ordinary skill in the art.
Unless clearly indicated to the contrary, the numerical parameters in the specification and claims of the present invention may be approximations that may vary depending upon the context in which the present invention is utilized. In particular, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as being modified in all instances by the term "about", and are intended to include variations of + -10%, in some embodiments + -5%, in some embodiments + -1%, in some embodiments + -0.5% by a particular amount. Furthermore, the word "comprising" does not exclude the presence of steps not listed in a claim. Ordinal numbers such as Arabic numerals, letters, etc. used in the specification and the claims are used to modify a corresponding step and do not indicate any ordinal number for that step nor the order of a certain step with another step.
Furthermore, unless specifically described or steps must occur in sequence, the order of the above steps is not limited to the list above and may be changed or rearranged according to the desired design. In addition, the above embodiments may be mixed with each other or other embodiments based on design and reliability, i.e. the technical features of the different embodiments may be freely combined to form more embodiments.
While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A non-methane total hydrocarbon clean-up catalyst composition comprising:
a first component: soluble ferrous sulfate, or a mixture of soluble ferrous sulfate and soluble manganese sulfate;
and a second component: alkaline earth metal hydroxides; wherein the alkaline earth metal hydroxide is Ba (OH) 2 And/or Sr (OH) 2 ；
And a third component: a manganese source compound;
wherein the molar ratio of the first component to the second component is in the range of 1:0.6-1:1; the molar ratio of the first component to the third component is in the range of 1:0.27 to 1:0.40.
2. The non-methane total hydrocarbon purification catalyst composition according to claim 1, wherein,
the manganese source compound is KMnO 4 、K 2 MnO 4 、NaMnO 4 And/or Na 2 MnO 4 The method comprises the steps of carrying out a first treatment on the surface of the And/or
The soluble sulfurFerrous acid is FeSO 4 ·7H 2 O、FeSO 4 ·6H 2 O and/or FeSO 4 ·5H 2 O; and/or
The soluble manganese sulfate is MnSO 4 ·4H 2 O and/or MnSO 4 ·H 2 O; wherein, in the mixture of the soluble ferrous sulfate and the soluble manganese sulfate, the mole percentage of the soluble manganese sulfate is between 5 percent and 50 percent.
3. The non-methane total hydrocarbon purification catalyst composition according to claim 2, wherein,
the first component is FeSO 4 ·7H 2 O；
The second component is Ba (OH) 2 ；
Wherein the FeSO 4 ·7H 2 O、Ba(OH) 2 、KMnO 4 The molar ratio of (1) (0.4-1.2) to (0.1-0.6).
4. The non-methane total hydrocarbon purification catalyst composition of claim 1, further comprising:
and a fourth component: titanium sol or silica sol.
5. A method for preparing a non-methane total hydrocarbon purification catalyst, which is characterized by comprising the following steps:
step A, carrying out solid-solid mixing grinding on a first component and a second component;
wherein the first component is soluble ferrous sulfate or a mixture of soluble ferrous sulfate and soluble manganese sulfate;
wherein the second component is an alkaline earth metal hydroxide, and the alkaline earth metal hydroxide is Ba (OH) 2 And/or Sr (OH) 2 ；
B, adding a third component into the material obtained in the step A for solid-solid mixing grinding;
wherein the third component is a manganese source compound;
step D, adding a binder and a pore-forming agent into the material obtained in the step B, and mixing, grinding, forming and drying to obtain a semi-finished catalyst;
and F, roasting the semi-finished catalyst to obtain the non-methane total hydrocarbon purifying catalyst.
6. The method according to claim 5, wherein the steps D and F further comprise:
step E, immersing the semi-finished catalyst into titanium sol or silica sol;
wherein if immersed in the titanium sol, the titanium sol attached to the semi-finished catalyst is calcined to form TiO on the surface of the non-methane total hydrocarbon purifying catalyst 2 A shell layer; if immersed in the silica sol, the silica sol attached to the semi-finished catalyst is calcined to form SiO on the surface of the non-methane total hydrocarbon purification catalyst 2 A shell layer.
7. The method of claim 6, wherein step E comprises:
immersing the semi-finished catalyst in a titanium sol in which TiO 2 The mass concentration of (2) is 0.02-2%.
8. The method according to claim 7, wherein,
in the step A, the first component is FeSO 4 ·7H 2 O, the second component is Ba (OH) 2 The method comprises the steps of carrying out a first treatment on the surface of the The solid-solid mixing grinding time is between 30 and 60 minutes; and/or
In the step B, the manganese source compound is KMnO 4 The solid-solid mixing grinding time is between 20 and 60 minutes; and/or
The step B and the step D further comprise the following steps: step C, washing and drying the material obtained in the step B to obtain a washed material; wherein, the drying is: drying at 100-120 deg.c for 1-10 hr or natural air drying for 12-24 hr; the step of adding the binder and the pore-forming agent into the material obtained in the step B in the step D comprises the following steps: c, adding a binder and a pore-forming agent into the water-washed material obtained in the step C; and/or
In the step D, the binder includes: an inorganic binder and an organic binder, wherein the inorganic binder is selected from one or more of the following materials: titanium sol, silica sol and aluminum sol, wherein the mass percentage of the titanium sol, the silica sol and the aluminum sol in the total amount of the materials after the inorganic binder is added is between 10% and 30%; the organic binder is selected from one or more of the following materials: carboxymethyl cellulose and sesbania gum; the mass percentage of the organic binder is between 0.01 and 0.4 percent of the total material after the organic binder is added; and/or
In the step D, the pore-forming agent is selected from one or more of the following materials: starch, flour; the mass percentage of the pore-forming agent accounting for the total amount of the materials after the pore-forming agent is added is between 0.1 percent and 5 percent; and/or
In the step D, the mixing and grinding time is 20-60 min; the drying is as follows: drying at 120 deg.c for 2-24 hr; and/or
In the step F, the roasting is: roasting at 350-700 deg.c for 1-4 hr.
9. A non-methane total hydrocarbon purification catalyst, characterized in that it is prepared by the preparation method according to any one of claims 5 to 8, and is in the form of particles or honeycombs.
10. Use of the non-methane total hydrocarbon purification catalyst composition according to any one of claims 1 to 4, or the non-methane total hydrocarbon purification catalyst according to claim 9, for removing non-methane total hydrocarbons from coke oven flue gas.
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