CN100341617C

CN100341617C - Chromium-free normal-temperature efficient purifying adsorbent for removing H2S or SO2 and preparing method thereof

Info

Publication number: CN100341617C
Application number: CNB021167400A
Authority: CN
Inventors: 马兰; 郭坤敏; 袁存乔; 刘进
Original assignee: 63971 Troops of PLA
Current assignee: 63971 Troops of PLA
Priority date: 2002-04-30
Filing date: 2002-04-30
Publication date: 2007-10-10
Anticipated expiration: 2022-04-30
Also published as: CN1454705A

Abstract

The present invention relates to desulfuration adsorbent which is prepared by that at least two kinds of transition metals, alkali metal compounds and polyacrylic ester which are respectively account for 3 to 30%, 1 to 40%, 0.2 to 10% of the weight of activated carbon carriers are immersed on special coal activated carbon. The preparation method comprises the steps that hydrosoluble transition metals, the potassium compounds and the polyacrylic ester are respectively immersed or immersed together on the activated carbon carriers, dried in the air at a temperature of 80 to 160 DEG C, and activated. The adsorbent has high desulfuration reaction rate, the capacity for purifying H2S and SO2 in the air can reach a ppb level, the space velocity can reach 50000h<-1> when the adsorbent is used, and the adsorbent has no chromium, and no ash on the surface, and is smooth, can be widely applied in semiconductor industry, the closed chamber of a special life support system, and the field of medical care, sanitation, cultural relic protection, environmental protection, etc.

Description

A kind of chromium-free normal-temperature efficient removes H 2S, SO 2The preparation method of purifying adsorbent

Affiliated technical field

The present invention relates to a kind of chromium-free normal-temperature efficient H ₂S, SO ₂Purifying adsorbent and preparation method thereof.

Background technology

Existing technology is to remove H separately ₂S, SO ₂Be main, remove SO as the activity oxidation manganese method ₂(Chen Zhaoxiong, environmental science 1996,16,3), its equipment complexity; Contain the iodine activated carbon method and take off SO ₂(Liu Dazhuan, Carbon1993,31,1), it generates sulfuric acid; The trickle bed reactor method is taken off SO ₂(Yuan Weikang, East China University of Science's journal, 1998,24,3), still under development; Chinese patent CN 1,137,556 1996, the improvement gas desulfurization method takes off H ₂S, it can only be used as thick desulfurization; Remove SO ₂With the patent of NOx US 5,366,710,1994 is arranged, it is with containing manganese and iron compound, and reaction temperature is 200 ℃.Normal temperature removes the patent CN1253847A of sulphur, and 2000, relate to H ₂S, COS and CS ₂, but do not comprise SO ₂, contain carcinogen chromium in its load component, and need high-temperature process under nitrogen protection in the preparation process.Chinese patent CN 1182716A, 1998, also be only to relate to H ₂S, COS and CS ₂,, and its load has carcinogen chromium.

Summary of the invention

The invention provides a kind of at normal temperature, the high air speed (50000h that uses ^-1) down can be with airborne H ₂S and SO ₂Purify simultaneously to the sorbent of extremely low concentration (ppb level), this sulfur-removing sorbent preparation technology is easy, desulphurization reaction speed fast and the smooth cleaning of this sorbent surface, does not contain carcinogen chromium.

Sorbent of the present invention is a carrier with the Special Coal activated carbon, and specific area is 1100～1200m ²/ g, the surface is rich in oxy radical; Load active component is more than one the water soluble compound among transition metal Fe, Co, Ni, V, Cu, Zn, Mo, the W, and addition is 0.3～30% of a carried by active carbon body weight; The water soluble compound KNO of alkali metal ₃, Na ₂CO ₃, among KI, LiCl, KOH, NaOH, the LiOH more than one,, addition is 1～40% of a carried by active carbon body weight; Be written into polyacrylate simultaneously, to overcome the powder phenomenon-tion after active carbon uses for a long time, the polyacrylate addition is 0.2～10% of a carried by active carbon body weight.

Sorbent preparation method of the present invention is as follows:

1, chooses the active carbon of appropriate bore structure, sieve, 130～150 ℃ of dryings more than 3 hours.

2, water soluble salt and the alkali-metal water soluble compound with transition metal is made into the certain density aqueous solution.

3, with 1 active carbon that makes by 50～85% water capacities with above-mentioned 2 solution impregnation, stir, shelved 3～24 hours, in air dry oven or fluidized bed furnace, in the air atmosphere dry 1～15 hour, temperature was 80～160 ℃.

4,3 Immesion active carbons that make are carried out smooth surface and handle, method is to add polyacrylate, and its amount promptly obtained sorbent of the present invention in dry 3～6 hours subsequently once more for vehicle weight 0.2～10%..

This desulphurization reaction speed of sulfur-removing sorbent provided by the present invention is fast, and the desulfurization conversion ratio is higher, has the H in purifying air ₂S, SO ₂Reach the ability of ppb level, use hourly space velocity can reach 50000h ^-1And do not contain the chromium that human body is had carcinogenesis, the surface is ashless, smooth, can be used for the exigent ultra-clean space air of air quality is purified, and the purification of sulphur-containing exhaust gas.Can be widely used in semi-conductor industry, extraordinary life-support system closed in space, and fields such as health care, historical relic's protection and environmental protection.

The specific embodiment

Embodiment 1

100 parts of ature of coal granular activated carbons, specific area 1100m ²/ g, the powder that sieves was 150 ℃ of dryings 3～5 hours.Cu (NO ₃) ₂2 parts, KOH is dissolved in 80 parts of water for 4 parts, mixes with above-mentioned active carbon, fully stirs, and makes its dipping evenly, places after 8 hours, puts in the baker in 130 ℃ of oven dry 6 hours.Make sorbent A.

Press embodiment 1 made sorbent A after long-term the use, a small amount of powder phenomenon-tion appears in activated carbon surface.

Embodiment 2

Press embodiment 1 preparation sorbent A, 2 parts of polyacrylate are dissolved in 60 parts of water, fully mix placement after 4 hours, in baker, dried 4 hours for 160 ℃ with A.Make sorbent B.Sorbent B smooth surface, no powder phenomenon-tion.

Embodiment 3

Fill in clarifier by embodiment 1 prepared sorbent A, at air speed 48000h ^-1, inlet gas concentration SO ₂=2.69ppb, H ₂During S=1.73ppb, test shows: purify back H ₂S and SO ₂, SO _xAll, see Table 1 less than 1ppb.

Table 1 uses sulfide concentration Monitoring Data in the air of desulfurizing agent of the present invention front and back

Before the use				After the use
Before the use				After the use				Time	SO _X(ppb)	SO ₂(ppb)	H ₂S(ppb)	Time	SO _X(ppb)	SO ₂(ppb)	H ₂S(ppb)
11:05	4.01	2.76	1.25	01:05	0.48	0.30	0.13	Time	SO _X(ppb)	SO ₂(ppb)	H ₂S(ppb)	Time	SO _X(ppb)	SO ₂(ppb)	H ₂S(ppb)
11:05	4.01	2.76	1.25	01:05	0.48	0.30	0.13	11:10	4.79	3.02	1.77	01:10	0.48	0.32	0.17
11:15	3.52	1.80	1.72	01:15	0.48	0.31	0.17	11:10	4.79	3.02	1.77	01:10	0.48	0.32	0.17
11:15	3.52	1.80	1.72	01:15	0.48	0.31	0.17	11:20	4.01	2.30	1.72	01:20	0.48	0.31	0.16
11:25	4.31	2.52	1.80	01:25	0.48	0.31	0.17	11:20	4.01	2.30	1.72	01:20	0.48	0.31	0.16
11:25	4.31	2.52	1.80	01:25	0.48	0.31	0.17	11:30	4.48	2.62	1.85	01:30	0.16	0.33	0.15
11:35	4.58	2.70	1.88	01:35	0.43	0.32	0.15	11:30	4.48	2.62	1.85	01:30	0.16	0.33	0.15
11:35	4.58	2.70	1.88	01:35	0.43	0.32	0.15	11:40	4.67	2.77	1.90	01:40	0.48	0.32	0.15
11:45	4.70	2.87	1.83	01:45	0.47	0.32	0.15	11:40	4.67	2.77	1.90	01:40	0.48	0.32	0.15
11:45	4.70	2.87	1.83	01:45	0.47	0.32	0.15	11:50	4.71	2.94	1.77	01:50	0.47	0.31	0.15
11:55	4.68	3.00	1.68	01:55	0.16	0.31	0.15	11:50	4.71	2.94	1.77	01:50	0.47	0.31	0.15
11:55	4.68	3.00	1.68	01:55	0.16	0.31	0.15	12:00	5.49	3.01	1.58	02:00	0.46	0.32	0.15
Mean value	4.42	2.69	1.73	Mean value	0.47	0.32	0.15	12:00	5.49	3.01	1.58	02:00	0.46	0.32	0.15

Embodiment 4

Fill in clarifier by embodiment 2 prepared sorbents, at air speed 48000h ^-1, SO ₂Concentration 3ppb, H ₂Under the S concentration 2ppb condition, after using in 688 days, H ₂S and SO ₂Respectively less than 1ppb and 2ppb.See Table 2.

Sulfide concentration Monitoring Data in the air behind the table 2 use desulfurizing agent of the present invention

Service time (my god)	668	670	672	674	676	678	680	682	684	686	688
Service time (my god)	668	670	672	674	676	678	680	682	684	686	688	SO ₂(ppb)	1.20	0.38	0.70	0.82	1.40	1.30	1.23	1.65	1.32	0.61	0.68
H ₂S(ppb)	0.40	0.22	0.30	0.33	0.36	0.28	0.31	0.41	0.36	0.32	0.33	SO ₂(ppb)	1.20	0.38	0.70	0.82	1.40	1.30	1.23	1.65	1.32	0.61	0.68

Claims

1, a kind of chromium-free normal-temperature efficient removes H ₂S, SO ₂The preparation method of purifying adsorbent, it is characterized in that the active carbon of choosing the appropriate bore structure sieves, 130～150 ℃ of dryings more than 3 hours, press active carbon 50%～85% water capacity, water soluble salt and alkali-metal water soluble compound with transition metal are made into certain density aqueous solution dipping, stir, shelve, after the drying, the Immesion active carbon that makes is added polyacrylate carry out the smooth surface processing, its consumption is 0.2%～10% of a vehicle weight, dry once more 3～6 hours subsequently, promptly obtain removing H ₂S, SO ₂Purifying adsorbent.

2, chromium-free normal-temperature efficient according to claim 1 removes H ₂S, SO ₂The preparation method of purifying adsorbent, the transition metal that it is characterized in that its load is more than one a water soluble compound among Fe, Co, Ni, V, Cu, Zn, Mo, the W, its load capacity is 0.3%～30% of a carried by active carbon body weight.

3, chromium-free normal-temperature efficient according to claim 1 removes H ₂S, SO ₂The preparation method of purifying adsorbent is characterized in that alkali-metal water soluble compound is KNO ₃, KI, KOH, LiCl, NaOH, LiOH.

4, chromium-free normal-temperature efficient according to claim 1 removes H ₂S, SO ₂The preparation method of purifying adsorbent is characterized in that dipping is 3～24 hours the time of shelving, and in air dry oven or fluidized bed furnace, in the air atmosphere dry 1～15 hour, temperature was 80 ℃～160 ℃.