CN102974359A

CN102974359A - Simultaneous desulfurization and denitration catalyst and preparation method thereof

Info

Publication number: CN102974359A
Application number: CN2012104630167A
Authority: CN
Inventors: 宋永吉; 史风华; 任晓光
Original assignee: Beijing Institute of Petrochemical Technology
Current assignee: Beijing Institute of Petrochemical Technology
Priority date: 2012-11-16
Filing date: 2012-11-16
Publication date: 2013-03-20

Abstract

The invention discloses a simultaneous desulfurization and denitration catalyst and preparation method of the simultaneous desulfurization and denitration catalyst. The desulfurization and denitration catalyst is composed of 60-80 parts by weight of carrier activated carbon (AC), 2-40 parts by weight of active ingredient neodymium oxide (Nd 203) and 0-20 parts by weight of promoter cobalt monoxide (CoO), wherein the total parts by weight of the activate ingredient and the prompter is 2-40. Detailed preparation method is explained in an introduction book. The simultaneous desulfurization and denitration catalyst and preparation method of the simultaneous desulfurization and denitration catalyst has the advantages of being wide in catalyst source, easy to obtain, easy in a preparation and regeneration method, high in catalyst mechanical strength, small in erosion, high in using efficiency of raw materials, suitable for mass production, high in catalyst activity, wide in operation temperature range, capable of being tested in a simulation test for a long time within a temperature range from 350 DEG C to 500 DEG C, and capable of acquiring a desulfurization denitration rate over 90 percent.

Description

A kind of while desulphurization denitration Catalysts and its preparation method

Technical field

The present invention relates to a kind of Catalysts and its preparation method, specifically desulphurization denitration catalyst of a kind of while and preparation thereof is used for smoke gas treatment.

Background technology

A large amount of consumption of the fossil fuel such as coal, oil, when promoting rapid economic development, the atmosphere polluting problem that brings is also day by day serious.Show that according to " China Environmental State Bulletin in 2011 " data national sulfur dioxide (SO2) emissions total amount was 2217.9 ten thousand tons in 2011, the discharged nitrous oxides total amount is 2404.3 ten thousand tons, and nitrogen oxide emission is in rising trend.SO ₂And NO _XA large amount of dischargings, serious harm ecological environment and human body are healthy, control atmosphere pollution is extremely urgent.

Both limited after the sulfur dioxide (SO2) emissions, expressly defined the discharge capacity of nitrogen oxide in country " the 12 " planning.Be control SO ₂And NO _XDischarging, at present domestic main employing desulfurization and denitrification integral technology is about to the integrated technique that independent desulfur technology and denitration technology carry out simple syndication.Wherein wet method lime stone (FGD) technology is mainly adopted in desulfurization, the method possess skills maturation, desulfuration efficiency advantages of higher, but exist also that floor space is large, operating cost is high, waste water and accessory substance gypsum secondary pollution problems; SCR (SCR) technology is then mainly adopted in denitration, and reducing agent is under the effect of catalyst, with NO _XBe reduced to the nitrogen G﹠W, catalyst is the core of SCR technology, V ₂O ₅/ TiO ₂And modified catalyst has obtained industrial applications.Yet the desulfurization and denitrification integral technology does not only solve the problems of independent desulfurization, and domestic SCR technology and catalyst system therefor almost all draw from external or rely on import, and investment and operating cost are very high.The desulphurization denitration technology can be with the SO in the flue gas in a process simultaneously ₂And NO _XThe technology that removes has simultaneously not only been saved the space device resource is effectively disposed, and the more important thing is that technique is simple, has reduced capital construction and operating cost.So exploitation simultaneously desulfurizing and denitrifying process will be the main trend of from now on smoke gas treatment technical development, associated catalysts and preparation method then are the focuses of work of this technique of exploitation.

Summary of the invention

The object of the invention is to overcome the weak point that traditional carbonaceous catalyst mechanical strength is low, easy to wear, the catalyst bed layer resistance is large, pressure is unequal, and a kind of while desulphurization denitration Catalysts and its preparation method is provided.

The objective of the invention is to implement by following measure:

A kind of while desulphurization denitration catalyst, this catalytic component comprises carrier active carbon AC, loads on the main active component Nd on the AC ₂O ₃With co-catalyst CoO, the parts by weight content of each component is in the catalyst: the Nd of the AC of 60～98 weight portions, 2～40 weight portions ₂O ₃With the CoO of 0～20 weight portion, wherein the total weight parts of active component and co-catalyst is 2～40.

A kind of preparation method of while desulphurization denitration catalyst comprises following sequential steps:

(1) preparation neodymium salt and cobalt salt mixed solution: according to the parts by weight of each component in the described catalyst, take by weighing neodymium salt after the conversion, cobalt salt is dissolved in the deionized water, be stirred to fully dissolving under the room temperature, can obtain used mixed solution, wherein used neodymium salt is: neodymium nitrate, acetic acid neodymium, cobalt salt are cobalt nitrate, cobalt acetate;

(2) catalyst prepares moulding: weighing polyvinyl alcohol is put into the mixed solution of step (1) gained, at 65～98 ℃, being stirred well to polyvinyl alcohol dissolves fully, then add activated carbon granule or powder, obtain catalyst pulp after stirring, continue again heating evaporation and fall part moisture, evaporation capacity is as the criterion to be fit to moulding, use as required at last different formers, can make graininess through extrusion modling, column, honeycombed catalyst, wherein the mean molecule quantity of used polyvinyl alcohol is 20000～200000, and its consumption is 0.1～10% of mixed solution quality;

(3) catalyst activation: at first the catalyst after the gained moulding in the step (2) is placed 80～150 ℃ of drying 2～8h, then under inert gas shielding, successively in 200～250 ℃ of roasting 1～4h, 600～1200 ℃ of roasting 1～8h obtain the catalyst finished product.

The present invention be directed in the flue gases such as thermal power plant, smeltery, oil plant and contain a large amount of SO ₂With the NO pollutant, develop desulphurization denitration catalyst in a kind of can between 350～500 ℃, the use, this catalyst can effectively be realized simultaneous catalytic reduction SO take CO as reducing agent ₂And NO _X, and reclaim elemental sulfur.

The present invention compared with prior art has following advantage: catalyst raw material wide material sources of the present invention, easily obtain, preparation and renovation process be simple; Mechanical strength is high, wearing and tearing are little, raw material availability is high, suitable for mass production; The present invention can remove the CO in the flue gas simultaneously take CO as reducing agent, and accessory substance is elemental sulfur, and the elemental sulfur that generates has been avoided product to be attached to and caused catalyst activity to reduce or inactivation on the catalyst with vapor state outflow catalyst bed; Catalyst activity of the present invention is high, good stability, but the operating temperature window is wide, and in the long-time simulated test in 350～500 ℃ of scopes, the desulphurization denitration rate all reaches more than 90%.

Description of drawings

Fig. 1 is 10%Nd of the present invention ₂O ₃NO/SO on the-5%CoO/AC catalyst ₂Conversion ratio and temperature concern schematic diagram.

The specific embodiment

1 following embodiment be to describe in further detail of the present invention, but the present invention is not subjected to the restriction of these embodiment.

Embodiment 1While desulphurization denitration catalyst n d ₂O ₃The preparation of-CoO/AC:

Take by weighing 11.5gNd (NO ₃) ₃5H ₂0 and 11.4gCo(NO ₃) ₂6H ₂0 is dissolved in the 80ml deionized water; and be heated to 75 ℃; then add the 10g molecular weight and be 80000 polyvinyl alcohol; being stirred to polyvinyl alcohol all dissolves; again the 50g active carbon powder is put into above-mentioned viscosity mixed solution and stirred; behind extruded moulding, in 80 ℃ of lower dry 6h, at last then in 150 ℃ of dryings, under nitrogen protection, successively make at last the bar column while desulphurization denitration catalyst 10%Nd of diameter 2cm length 2～5cm at 200 ℃ of lower roasting 2h, 900 ℃ of lower roasting 4h ₂O ₃-5%CoO/AC, i.e. AC, Nd ₂O ₃Be respectively 85,10 and 5 with the weight portion of CoO, this specific surface area of catalyst is 361.9m ²G ^-1

Catalyst is investigated the catalytic activity of simulated flue gas:

Get the catalyst among the embodiment 1, place on the support of fixed bed reactors constant temperature zone, smoke components is: 2500ppmCO, 1000ppmSO ₂, 500ppmNO, nitrogen are Balance Air, air speed is 4000h ^-1, investigating temperature range is 300～500 ℃, and temperature is by the control of temperature programming instrument, and experimental result sees Table 1 and Fig. 1.

Can be found out that by table 1 and Fig. 1 when temperature rose to 300 ℃, this catalyst activity improved rapidly, SO in the time of 330 ℃ ₂With the conversion ratio of NO all above 90%, catalyst activities tend towards stability after 350 ℃, between 350～500 ℃, SO ₂With the conversion ratio of NO all above 95%.

Table 1 10%Nd ₂O ₃NO/SO on the-5%CoO/AC catalyst ₂Conversion ratio

Claims

1. desulphurization denitration catalyst simultaneously, this catalytic component comprises carrier active carbon AC, loads on the main active component Nd on the AC ₂O ₃With co-catalyst CoO, it is characterized in that: the parts by weight content of each component is in this catalyst: the Nd of the AC of 60～98 weight portions, 2～40 weight portions ₂O ₃With the CoO of 0～20 weight portion, wherein the total weight parts of active component and co-catalyst is 2～40.

2. the preparation method of a kind of while desulphurization denitration catalyst as claimed in claim 1, it is characterized in that: the method comprises following sequential steps:

(2) catalyst prepares moulding: weighing polyvinyl alcohol is put into the mixed solution of step (1) gained, under 65～98 ℃, being stirred well to polyvinyl alcohol dissolves fully, then add activated carbon granule or powder, obtain catalyst pulp after stirring, continue again heating evaporation and fall part moisture, evaporation capacity is as the criterion to be fit to moulding, use as required at last different formers, can make graininess through extrusion modling, column, honeycombed catalyst, wherein the mean molecule quantity of used polyvinyl alcohol is 20000～200000, and its consumption is 0.1～10% of mixed solution quality;

(3) catalyst activation: at first with the catalyst after the gained moulding in the step (2); place 80～150 ℃ of drying 2～8h, then under inert gas shielding, successively in 200～250 ℃ of roasting 1～4h; 600～1200 ℃ of roasting 1～8h obtain the catalyst finished product.