CN104984648B

CN104984648B - A kind of method of wet-dry change Combined Treatment navajoite sodium roasting tail gas

Info

Publication number: CN104984648B
Application number: CN201510303351.4A
Authority: CN
Inventors: 李浩然; 刘鹏伟; 杜竹玮; 杨鑫龙; 孙铭; 王琪
Original assignee: Institute of Process Engineering of CAS
Current assignee: Institute of Process Engineering of CAS
Priority date: 2015-06-04
Filing date: 2015-06-04
Publication date: 2017-06-13
Anticipated expiration: 2035-06-04
Also published as: CN104984648A

Abstract

The invention discloses a kind of method of wet-dry change Combined Treatment navajoite sodium roasting tail gas, including chlorine-solidifying agent and sodium salt additive are added into pelletizing in navajoite, the sodium roasting in shaft furnace, lower furnace portion temperature is higher than top, furnace gas is moved upwards in stove, it is in countercurrent flow between furnace charge, it is higher than chlorine-solidifying agent using sodium salt additive decomposition temperature, lower furnace portion decomposes the chlorine-solidifying agent absorption that the tail gas for producing is decomposed by upper furnace, reactant is absorbed with residual exhaust by two-stage absorption carrier and alkali lye spray equipment, through wash-out after absorption carrier saturation, can be recycled, eluent can be utilized for precipitation is crystallized.Present invention process is simple, and tail gas absorption speed is high, and process continuity is good, and waste gas is easy to recycle, and environmental protection has a extensive future.

Description

A kind of method of wet-dry change Combined Treatment navajoite sodium roasting tail gas

Technical field

The present invention relates to the treatment of navajoite sodium roasting vanadium-extracting tail gas, more particularly to a kind of wet-dry change Combined Treatment navajoite sodium Change the method that baking tail gases and product are utilized by post-order process.

Background technology

Vanadium is a kind of important strategic resource, and China is vanadium resource big country, and wherein bone coal, clay vanadium mineral are distinctive China Advantage navajoite resource, accounts for the 87% of domestic total vanadium amount.Sodium roasting vanadium-extracting technique, because of its process is simple, vanadium high conversion rate is Generally use both at home and abroad.But can produce substantial amounts of dusty gas (C1 in roasting₂And HCl), problem of environmental pollution is protruded, and opposite Product equipment causes heavy corrosion.The technique for studying navajoite sodium roasting vent gas treatment, has great to current navajoite vanadium extraction industry Realistic meaning, be also realize navajoite vanadium extraction industry clean manufacturing and sustainable development only way.

Treatment navajoite sodium roasting tail gas conventional method has alkali lye three-level spray process, the two sections of suctions of water and NaOH at present Receipts method, lime cream absorption method, water and frerrous chloride elution method etc., but exist that reagent cost is high, and exothermic heat of reaction need to set cooling Device, operating cost is high, after tail gas absorption the shortcomings of recycling high cost.Therefore, how high efficiency, low cost, green ring Ground treatment sodium roasting tail gas is protected, the sustainable development to vanadium industry has far-reaching significance.

The content of the invention

The object of the invention is mainly to provide a kind of wet-dry change Combined Treatment navajoite sodium roasting tail gas, and product is by postorder The method of technology utilization, and overcome existing navajoite sodium roasting exhaust gas treating method high cost, the problems such as tail gas is difficult by, carries For a kind of high efficiency, low cost, the process of green treatment navajoite sodium roasting tail gas.

The process of the wet-dry change Combined Treatment navajoite sodium roasting tail gas that the present invention is provided, including the steps：

(1) chlorine-solidifying agent, sodium salt additive are taken to be well mixed with navajoite and pelletizing, and pellet reaction are added in shaft furnace, And air is passed through during the course of the reaction；

Preferably, the navajoite is crushed to granularity for 40-500 mesh.

(2) gas of discharge in step (1) is passed through in the absorption carrier of two-stage absorption, then is entered by alkali lye spray equipment One step absorbs tail gas.

Absorption carrier herein can be the carrier for possessing porous honeycomb structure that those skilled in the art often use, its Can be used for adsorbent particles dust.

(3) after the absorption carrier saturation during step (2) two-stage absorbs, eluted, carrier loop is used.

Preferably, chlorine-solidifying agent is ammonium salt class combination medicament in step (1), is 1 with the mass ratio of navajoite:20~1:10.

Preferably, sodium salt additive is NaCl, Na in step (1)₂CO₃And Na₂SO₄Composition, combination medicament and navajoite Mass ratio be 1:5~1:10.

It is furthermore preferred that NaCl, Na in the sodium salt additive₂CO₃And Na₂SO₄Mass ratio be 1-3:1-3:1-3.

Preferably, pelletizing quality is 50~100g, 2~5cm of pelletizing diameter in step (1).

Preferably, the reaction time is 3~6h in step (1), and heating rate is 10~20 DEG C/min.

Preferably, reaction temperature is 700~900 DEG C in step (1).

Preferably, the throughput of air is 40~200L/h in step (1).

Preferably, absorption carrier is absorbed using two-stage in step (3), is eluted after adsorption saturation.

Preferably, contain ammonium chloride in the eluent in step (4) after absorption carrier adsorption saturation wash-out, it is concentrated after can For precipitation crystallization.

Preferably, alkali lye cyclic absorption tail gas in alkali lye spray equipment in step (3).

In the present invention, in 600 DEG C of decomposition, chlorine-solidifying agent is decomposed sodium salt additive at 400 DEG C, using sodium during sodium roasting Salt additives decomposition temperature is higher than chlorine-solidifying agent, and lower furnace portion decomposes the chlorine-solidifying agent absorption that the tail gas for producing is decomposed by upper furnace, Reactant is absorbed with residual exhaust by two-stage absorption carrier and alkali lye spray equipment, after absorption carrier saturation, through wash-out, is recycled Use, eluent can be utilized for precipitation is crystallized.Present invention process is simple, and tail gas absorption speed is high, and process continuity is good, and waste gas is just In recycling, environmental protection has a extensive future.

Brief description of the drawings

Fig. 1 is a kind of wet-dry change Combined Treatment navajoite sodium roasting tail gas process flow chart.

Accompanying drawing is identified：

1-charging aperture；2-pellet；3-heating zone；4-air inlet；5-discharge port；6-waste gas gas outlet； 7-absorption carrier；8-alkali lye spray column；9-circulating pump.

Specific embodiment

Specific embodiment of the invention is the following is, it is used only as illustrating rather than limitation for the application.

Referring to Fig. 1, chlorine-solidifying agent is commercially available ammonium salt class chlorine-solidifying agent, and it can fix hydrogen chloride in tail gas and chlorine.The present invention Absorbed using two-stage absorption carrier and alkali lye spray column, the absorption carrier that it is used is possessing that those skilled in the art often use The carrier of porous honeycomb structure, it can be used for adsorbent particles dust, originate as commercially available, because the treatment for tail gas is ability Field technique personnel frequently with technological means, those skilled in the art can also select other conventional carriers for processing tail Gas.Be can be recycled after absorption carrier adsorption saturation wash-out, eluent can be used for precipitation crystallization.Whole technique cleaning, efficient, letter Just.

Embodiment 1

Guangxi Rock coal containing alum, bone coal XRF elementary analysis results are as follows：

Na	Mg	Al	Si	P	S	K	Ca	Ti	V	Mn	Fe
												0.096	2.176	15.585	60.442	0.079	8.022	3.737	0.039	0.660	1.434	0.076	2.748
Ni	Cu	Ga	As	Se	Rb	Sr	Y	Zr	Mo	Pb	Cl
												0.025	0.035	0.003	2.114	0.004	0.016	0.005	0.006	0.021	0.011	0.011	2.652

By bone coal ore grinding 10 minutes, chlorine-solidifying agent and sodium salt additive NaCl, Na are separately added into₂CO₃、Na₂SO₄, and mix equal It is even, wherein chlorine-solidifying agent content 4%, NaCl contents 4%, Na₂CO₃Content 4%, Na₂SO₄Content 2%；By mixed sample pressure Ball, the weight of single ball is in 60g or so.

Dried after pressure ball molding, 900 DEG C of sodium roasting roasting temperature 4 hours is carried out in shaft furnace, in roasting process not It is open close enter a certain amount of air, throughput is 50L/h, and tail gas is absorbed by two-stage absorption carrier and alkali lye spray equipment, and absorption is carried Body be can be recycled in adsorption saturation after wash-out, and level vector can be circulated through three circulations, two grade carriers through four times.Wash-out Liquid is crystallized for precipitation, can reduce the medicament of consumption 6%.After testing, hydrogen chloride and chlorine waste gas absorb through secondary absorption carrier X Purifying rate reaches 79.6%, then is sprayed through alkali lye, and gross decontamination rate reaches 96.3%.

Embodiment 2

Hubei bone coal slag navajoite, bone coal XRF elementary analysis results are as follows：

Na	Mg	Al	Si	P	S	K	Ca	Ti	V	Mn
											0.054	0.187	1.73	37.03	0.129	1.22	0.445	0.518	0.1	0.549	0.005
Fe	Ni	Cu	Zn	Ba	Cr	Pb	Sr	Zr	Mo	Cl
											1.11	0.0257	0.048	0.173	3.57	0.0361	0.006	0.024	0.0026	0.003	0.034

By clay vanadium mineral ore grinding 8 minutes, chlorine-solidifying agent and sodium salt additive NaCl, Na are separately added into₂CO₃、Na₂SO₄, and mix Close uniform, wherein chlorine-solidifying agent content 8%, NaCl contents 6%, Na₂CO₃Content 2%, Na₂SO₄Content 2%；By mixed sample Product pressure ball, the weight of single ball is in 60g or so.

Dried after pressure ball molding, 800 DEG C of sodium roasting roasting temperature 5 hours is carried out in shaft furnace, in roasting process not It is open close enter a certain amount of air, throughput is 100L/h, and tail gas is absorbed by two-stage absorption carrier and alkali lye spray equipment, and absorption is carried Body adsorption saturation be can be recycled after wash-out, and level vector can be circulated through three circulations, two grade carriers through four times.Eluent For precipitation crystallization, the medicament of consumption 9% can be reduced.After testing, hydrogen chloride and chlorine waste gas are net through secondary absorption carrier absorption Rate reaches 86.5%, then is sprayed through alkali lye, and gross decontamination rate reaches 97.8%.

Embodiment 3

Yunxi of Hubei's clay vanadium mineral, mineral XRF elementary analysis results are as follows：

Na	Mg	Al	Si	P	S	K	Ca	Ti	V	Fe	Pb
												0.134	1.362	9.625	79.162	1.373	0.279	1.236	0.69	0.259	1.722	2.183	0.012
Ni	Cu	Zn	As	Se	Rb	Sr	Y	Zr	Mo	Ba	Cl
												0.025	0.1	0.058	1.322	0.002	0.003	0.029	0.02	0.01	0.005	0.124	0.016

By clay vanadium mineral ore grinding 12 minutes, chlorine-solidifying agent and sodium salt additive NaCl, Na are separately added into₂CO₃、Na₂SO₄, and mix Close uniform, wherein chlorine-solidifying agent content 8%, NaCl contents 4%, Na₂CO₃Content 4%, Na₂SO₄Content 2%；By mixed sample Product pressure ball, the weight of single ball is in 60g or so.

Dried after pressure ball molding, 800 DEG C of sodium roasting roasting temperature 5 hours is carried out in shaft furnace, in roasting process not It is open close enter a certain amount of air, throughput is 100L/h, and tail gas is absorbed by two-stage absorption carrier and alkali lye spray equipment, and absorption is carried Body adsorption saturation be can be recycled after wash-out, and level vector can be circulated through three circulations, two grade carriers through four times.Eluent For precipitation crystallization, the medicament of consumption 10% can be reduced.After testing, hydrogen chloride and chlorine waste gas are net through secondary absorption carrier absorption Rate reaches 89.62%, then is sprayed through alkali lye, and gross decontamination rate reaches 98.97%.

Embodiment 4

Chengde vanadium titano-magnetite, vanadic anhydride grade is 0.7%.

By titanomagnetite ore grinding 10 minutes, chlorine-solidifying agent and sodium salt additive are separately added into, be well mixed, wherein chlorine-solidifying agent contains Amount 10%, NaCl contents 4%, Na₂CO₃Content 4%, Na₂SO₄Content 2%；By mixed sample pressure ball, the weight of single ball In 60g or so.

Dried after pressure ball molding, 800 DEG C of sodium roasting roasting temperature 4 hours is carried out in shaft furnace, in roasting process not It is open close enter a certain amount of air, throughput is 120L/h, and tail gas is absorbed by two-stage absorption carrier and alkali lye spray equipment, and absorption is carried Body adsorption saturation be can be recycled after wash-out, and level vector can be circulated through three circulations, two grade carriers through four times.Eluent For precipitation crystallization, the medicament of consumption 8% can be reduced.After testing, hydrogen chloride and chlorine waste gas are net through secondary absorption carrier absorption Rate reaches 88.3%, then is sprayed through alkali lye, and gross decontamination rate reaches 98.7%.

Claims

1. a kind of method of wet-dry change Combined Treatment navajoite sodium roasting tail gas, including the steps：

(1) chlorine-solidifying agent, sodium salt additive are taken to be well mixed with the navajoite of milled and pelletizing, and adds pellet anti-in shaft furnace Should, and air is passed through during the course of the reaction, the sodium salt additive decomposition temperature is higher than chlorine-solidifying agent；

(2) gas of discharge in step (1) is passed through in the absorption carrier of two-stage absorption, then it is further by alkali lye spray equipment Absorb tail gas；

(3) eluted after the absorption carrier saturation during step (2) two-stage absorbs；

The chlorine-solidifying agent is ammonium salt class combination medicament, is 1 with the mass ratio of navajoite:20~1:10；

Reaction temperature is 700~900 DEG C in the step (1).

2. method according to claim 1, it is characterised in that sodium salt additive is NaCl, Na in step (1)₂CO₃With Na₂SO₄Combination medicament, its mass ratio with navajoite is 1:5~1:10.

3. method according to claim 1, it is characterised in that the pellet quality that pelletizing is obtained in step (1) is 50~ 100g, 2~5cm of pelletizing diameter.

4. method according to claim 1, it is characterised in that the reaction time is 3~6h in step (1), and heating rate is 10~20 DEG C/min.

5. method according to claim 1, it is characterised in that throughput is 40~200L/h in step (1).

6. method according to claim 1, it is characterised in that absorption carrier makes in zeolite regeneration Posterior circle in step (3) With.

7. method according to claim 1, it is characterised in that washing after absorption carrier adsorption saturation wash-out in step (3) As precipitation crystallization after de- liquid is concentrated.

8. method according to claim 1, it is characterised in that alkali lye cyclic absorption in alkali lye spray equipment in step (2) Tail gas.