CN110550680B - Method for preventing multi-effect concentration and one-effect scaling of titanium dioxide waste acid produced by sulfuric acid process - Google Patents
Method for preventing multi-effect concentration and one-effect scaling of titanium dioxide waste acid produced by sulfuric acid process Download PDFInfo
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Abstract
The invention discloses a method for preventing multi-effect concentration and one-effect scaling of titanium dioxide waste acid produced in a sulfuric acid process, which comprises the steps of directly feeding 20-30% (including rotary kiln tail gas preconcentration) waste acid produced in a titanium dioxide production workshop into a preheater and a one-effect heater without pretreatment, heating the waste acid at 103-106 ℃ and under the vacuum degree of 48-52 KPa, adding concentrated finished acid or secondary-effect concentrated acid overflowing into a ripening tank into a one-effect concentration system according to the acid amount proportion of the one-effect concentrated acid, and achieving dynamic balance under the condition that the acid content is stabilized to be more than 38%, wherein FeSO4.7H in the waste acid2O、CaSO4.2H2O, instant dehydration; the dissolved matters of Fe and Ca plasma sulfate are reduced along with the solubility, and can be regarded as autogenous crystal seeds combined with homophase salt to generate solid-phase precipitates, so that the condition that Fe and Ca plasma dissolves sulfate and is attached to the low-end interface and the high-end interface of the temperature gradient to form layer scale mainly comprising calcium sulfate and bridging of Fe salt is avoided.
Description
Technical Field
The invention relates to the technical field of waste acid treatment in titanium dioxide production by a sulfuric acid method, in particular to a method for preventing multiple-effect concentration and one-effect scaling of titanium dioxide waste acid by the sulfuric acid method.
Background
Titanium dioxide is widely applied to various industries and has large demand. At present, the titanium dioxide is mainly produced by a sulfuric acid method, a chlorination method and a hydrochloric acid method, 90% of titanium dioxide in China is produced by the sulfuric acid method, waste acid is generated in the production process of the titanium dioxide, 6-7 tons of waste acid is discharged when 1 ton of titanium dioxide is produced, the waste acid contains about 20% of salts such as sulfuric acid, ferrous sulfate, calcium sulfate and the like, insoluble titanium dioxide, soluble titanium and the like, a large amount of impurities limit the long-period stable operation of the titanium dioxide waste acid concentration process, and a recovery concentration device is complex in treatment process and high in difficulty. The treatment of waste acid is related to the yield of titanium dioxide sulfuric acid consumption, so that the economic benefit is influenced, and simultaneously, a large amount of titanium gypsum generated by neutralizing the waste acid is related to the environmental protection problem, so that the survival and development of the titanium dioxide industry of the sulfuric acid process are influenced.
The main treatment method for treating waste acid at present comprises the following steps: (1) transport to open sea for discharge, but is prohibited due to environmental requirements; (2) the method is used for steel plants to wash steel plates, produce gypsum by lime neutralization and produce ammonium sulfate by ammonia water neutralization, but the utilization rate is very low; (3) concentrating and recycling waste acid; (4) the comprehensive utilization is carried out by qualified operators.
The concentration of waste acid is the most resource-saving and environment-friendly treatment scheme, and the existing treatment method is that the waste acid and the waste acid are synchronously treated, namely, the concentration of sulfuric acid is improved by concentration and salt slag is precipitated. Two methods are currently adopted for deslagging: (1) the 98% concentrated sulfuric acid and the 20% waste acid are directly mixed to form 60% acid, a large amount of salt is separated out, and the method needs to consume a large amount of concentrated sulfuric acid; (2) by adopting a multi-effect evaporation concentration method, waste acid (with the concentration of 20-30 percent and insoluble TiO) generated in the production process of titanium dioxide by a sulfuric acid method is adopted2Concentration lower than 0.2 g/l) and pumped to a storage tank for standby before concentration. The waste acid is fed into a waste acid concentration device after being metered by a storage tank feed pump, enters a primary-effect negative pressure evaporation system through a preheater, is heated and flash-evaporated and concentrated by using saturated steam, secondary steam generated in the primary-effect concentration process of the waste acid is used as a heat source of a secondary-effect preheater, and secondary steam condensate is collected through a liquid seal tank. Circulating liquid of the first-effect evaporator enters a second-effect negative-pressure evaporation system through overflow, the circulating liquid overflows into a ripening tank after being evaporated and concentrated to be qualified through second-effect negative pressure, the concentrated finished acid is subjected to solid-liquid separation after being cooled and crystallized in the ripening tank, the concentrated finished acid is obtained and reused in the acidolysis process of titanium dioxide production, and the separated solid ferrous hydrate is comprehensively utilized.
Preheating about 20-30% of concentration in the traditional process, and then performing primary effect, wherein the waste acid is concentrated to 31-33%, the temperature is 108 ℃, and the vacuum degree is 39-43 kPa; in the second stage, the mass fraction of the waste acid is concentrated from 31 to 33 percent to 51 to 53 percent, the temperature is 86 ℃, and the vacuum degree is 85 to 88 kPa. The method has the disadvantages that in the concentration process, along with the increase of the acid concentration, salts, particularly calcium salt and ferrous salt are continuously separated out, so that equipment and pipelines are seriously blocked, frequent parking cleaning or mechanical cleaning is required for ensuring normal operation, the period is shorter and shorter, finally, even the operation time of driving is not long, the equipment utilization rate is low, the operation cost is high, the labor intensity is high, and the operation is very troublesome.
Although the problem of scaling and blocking can be solved by using single-effect concentration, the mass fraction of waste acid is concentrated by 55-65%, the steam quantity in a concentration unit is large, and the comprehensive cost is high, so that the single-effect concentration cannot be accepted by every titanium dioxide production enterprise.
Disclosure of Invention
In order to solve the problems, the invention provides a method for preventing scaling of one-effect in the multi-effect concentration process of titanium white waste acid by a sulfuric acid method, wherein in the process of waste acid concentration, a large amount of metal salt is separated out in the one-effect concentration process by accurately controlling process parameters, so that continuous production can be realized, scaling on the inner wall of a pipeline and a system can be avoided, and long-period start-up of a waste acid concentration device can be realized.
The invention is realized by the following technical scheme:
a method for preventing multi-effect concentration and one-effect scaling of titanium dioxide waste acid produced by a sulfuric acid process comprises the following steps:
(1) directly adding titanium white waste acid with the concentration of 20-30% into a first-effect concentration system, adding concentrated sulfuric acid to keep the concentration in the first-effect concentration system at 38-42%, wherein the temperature of a first-effect evaporator is 103-106 ℃, the vacuum degree is 52-48 kpa, and sulfuric acid overflows into a second-effect concentration system after the first-effect concentration;
(2) the vacuum degree of the double-effect concentration system is kept at 88-92 kpa, the temperature is 78-76 ℃, the concentration of concentrated sulfuric acid is 53-55%, impurities are removed through plate-and-frame filter pressing, and the concentrated finished acid can be continuously concentrated or reused for titanium dioxide production.
Preferably, the iron-titanium ratio of the titanium liquid in the titanium white production is 0.26-0.42.
The iron-titanium ratio is the total iron content and the total TiO in the titanium liquid2The content ratio is expressed as the following formula that the total Fe content (g/l) iron-titanium ratio = the total Fe content (g/l)/the total TiO2The high and low iron-titanium ratio of the content (g/l) has certain influence on the particle size and the structure of metatitanic acid of a hydrolysate.
Preferably, the concentration of the titanium white waste acid is 22-25%.
Preferably, the concentrated finished acid is added into the single-effect concentration system or the sulfuric acid obtained by using the double-effect concentration overflow without separation is used from the viewpoint of energy conservation.
Preferably, the concentration of the sulfuric acid in the one-effect concentration system is 38%, the temperature is 103 ℃, and the vacuum degree is 52 kpa.
Preferably, the temperature of the double-effect concentration system is 76.5 ℃, and the vacuum degree is 91 kpa.
The invention mainly aims at waste acid generated in the production process of titanium dioxide by a sulfuric acid method, the inner wall of a pipeline is easy to scale in the concentration evaporation treatment process, in the general waste acid concentration treatment process, the concentration of sulfuric acid in a one-effect evaporator is 31%, the temperature is 108 ℃, and the vacuum degree is 39-43 kpa, but a layer of thick scale can be formed on the inner wall of the pipeline due to slow precipitation of calcium salt, ferric salt and titanium salt in the waste acid, and the thickness is thicker and thicker along with accumulation of time, so that the pipeline is blocked, the inner wall is blocked, the heat transfer effect of a heater is reduced, and the normal production is seriously influenced. The iron salt in the waste acid can be mostly removed by sedimentation and filtration before concentration, but the calcium salt cannot be removed, and flocculent crystals are generated in the concentration process and are attached to the inner wall of the pipeline to form calcium scale.
According to the invention, most of metal salt in the waste acid is not required to be removed before concentration, but is removed in the concentration process, 20-30% (including rotary kiln tail gas preconcentration) of the waste acid generated in a titanium white production workshop can directly enter a preheater and a one-effect heater for heating without pretreatment, the temperature is 103-106 ℃, the vacuum degree is 48-52 KPa, and the acid content is stabilized at more than 38%Reach dynamic balance under the condition of (1), and FeSO in waste acid4·7H2O、CaSO4·2H2O, instant dehydration; along with the reduction of the solubility, Fe and Ca plasma sulfate is separated out in a solid particle form and can be regarded as autogenous crystal seeds to be combined with homophase salt to generate solid-phase precipitate, so that the sulfate dissolved out by Fe and Ca plasma is prevented from being implanted at the low-end interface and the high-end interface of the temperature gradient to form layer scale mainly comprising calcium sulfate and bridging of Fe salt. The waste acid is adjusted to be in a certain concentration, pressure and temperature range, so that the metal salt is dehydrated instantly and separated out in a large amount to form large particles, and the phenomenon that the metal salt is slowly separated out, scales are formed in the inner walls of pipelines and equipment, and the pipelines are blocked is avoided. The large particles separated out enter a double-effect evaporator in an overflow mode, conditions also need to be controlled in the double effect, sulfuric acid is further concentrated and recycled, and the formed large particles are removed through plate-and-frame filter pressing.
Advantageous effects
A method for preventing sulfate process titanium dioxide waste acid from multiple-effect concentration and one-effect scaling is characterized in that the vacuum of a one-effect evaporator is increased from 40KPa to 48 KPa; the acid content of the one-effect concentration evaporation system is increased to 38% -42%; meanwhile, in order to ensure that the acid content of the first-effect concentration system is stabilized to be more than 38%, a first-effect acid concentration auxiliary device is additionally designed, acid of a concentrated finished product or acid of secondary-effect overflow into the ageing tank is added into the first-effect concentration system according to the proportion of the amount of the first-effect concentrated acid, so that the large fluctuation of the acid content in the first-effect concentration process is reduced, and the dynamic balance of the first-effect acid concentration is realized; by improving the first-effect concentration evaporation state, the first-effect vacuum degree is improved, and the dynamic balance of first-effect steam, second-effect steam, concentrated acid amount and a vacuum system is established; in the continuous concentration process of the waste acid, the inner wall of the pipeline can not be scaled, and the shutdown descaling and maintenance are not needed, so that the economic loss is reduced, the concentrated sulfuric acid can be reused for titanium dioxide production, the process is simple and easy to implement, and the application prospect is wide. And the reduction of temperature in the process of one-effect concentration also reduces the consumption of energy.
Drawings
FIG. 1A diagram of a non-fouled pipe in example 1;
FIG. 2 is a schematic representation of a fouled pipe in comparative example 1;
FIG. 3 is a layer scale pattern for the scale formed in comparative example 1;
FIG. 4: the flow chart of the device adopted by the embodiment.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Titanium dioxide waste acid with the sulfuric acid concentration of 23 percent is preheated, and then the titanium dioxide waste acid (with the iron-titanium ratio of 0.28) is introduced into a first-effect concentration system, a second-effect concentrated solution with the concentration of 55 percent is added, the sulfuric acid concentration in the first-effect concentration system is maintained at 38 percent, the temperature is 103 ℃, the vacuum degree is 52kpa, at the moment, a large amount of salt can be separated out to form large particles, the sulfuric acid in the first-effect concentration system overflows into the second-effect concentration system, the temperature of the second-effect concentration system is maintained at 76.5 ℃, the vacuum degree is 91kpa, the sulfuric acid is concentrated to the concentration of 53 percent, and the large particles. The inner wall of the pipeline of the equipment can not generate the scaling phenomenon in the continuous production process, and the time and the cost are saved without overhauling, stopping and descaling. It can be seen in fig. 1 that the inner wall of the pipe is not fouled.
Example 2
Titanium dioxide waste acid with the sulfuric acid concentration of 20 percent is preheated, and then the titanium dioxide waste acid (with the iron-titanium ratio of 0.30) is introduced into a first-effect concentration system, concentrated sulfuric acid with the concentration of 98 percent is added, the sulfuric acid concentration in the first-effect concentration system is maintained at 42 percent, the temperature is 106 ℃, the vacuum degree is 52kpa, at the moment, a large amount of salt can be separated out to form large particles, sulfuric acid in the first-effect concentration system overflows into a second-effect concentration system, the temperature of the second-effect concentration system is maintained at 78 ℃ and the vacuum degree is 88kpa, the sulfuric acid is concentrated to the sulfuric acid with the concentration of 55 percent. The inner wall of the pipeline of the equipment can not generate the scaling phenomenon, and the time and the cost are saved without overhauling, stopping and scaling.
Example 3
Titanium dioxide waste acid with the sulfuric acid concentration of 30 percent is preheated, and then the titanium dioxide waste acid (with the iron-titanium ratio of 0.42) is introduced into a first-effect concentration system, a second-effect concentrated solution with the concentration of 55 percent is added, the sulfuric acid concentration in the first-effect concentration system is maintained at 40 percent, the temperature is 104 ℃, the vacuum degree is 50kpa, at the moment, a large amount of salt can be separated out to form large particles, the sulfuric acid in the first-effect concentration system overflows into the second-effect concentration system, the temperature of the second-effect concentration system is maintained at 77 ℃, the vacuum degree is 90kpa, the sulfuric acid is concentrated to the concentration of 54 percent, and the salt of. The inner wall of the pipeline of the equipment can not generate the scaling phenomenon, and the time and the cost are saved without overhauling, stopping and scaling.
Comparative example 1 (ordinary concentration process)
Titanium dioxide waste acid with the sulfuric acid concentration of 23 percent (the iron-titanium ratio is 0.28) is preheated and then introduced into a one-effect concentration system, the sulfuric acid concentration in the one-effect concentration system is kept at 31 percent, the temperature is 108 ℃, the vacuum degree is 40kpa, salt is separated out at the moment, but a layer of thick calcium scale is formed at the position where liquid is contacted with the pipeline wall, the sulfuric acid in a one-effect concentrator overflows into a two-effect evaporator, the temperature of the two-effect evaporator is kept at 86 ℃, the vacuum degree is 88kpa, and the sulfuric acid is concentrated to the sulfuric acid with the concentration of 51 percent. In the production process, layer scale mainly comprising calcium sulfate and bridging of Fe salt can be formed in a pipeline or a concentration system; see fig. 2 and 3.
Comparative example 2 (sulfuric acid concentration was adjusted in advance in the ordinary concentration process)
Titanium dioxide waste acid with the sulfuric acid concentration of 23 percent (the iron-titanium ratio is 0.28) is mixed with 98 percent concentrated sulfuric acid to form 60 percent sulfuric acid before being introduced into the one-effect concentration system, a large amount of salt is precipitated at the moment, the sulfuric acid is introduced into the one-effect concentration system after being filtered, the sulfuric acid concentration in the one-effect concentration system is 31 percent at the moment, the temperature is 108 ℃, the vacuum degree is 40kpa, and calcium scale is still formed at the position where liquid is in contact with the inner wall of the pipeline and the inner wall of equipment to influence the heat transfer of the pipeline and the inner wall of the equipment.
Comparative example 3 (concentration 35%, also scaling)
Titanium dioxide waste acid with the sulfuric acid concentration of 23 percent (the iron-titanium ratio is 0.28) is preheated and then is introduced into an one-effect concentration system, the sulfuric acid concentration in the one-effect concentration system is kept at 35 percent, the temperature is 108 ℃, the vacuum degree is 40kpa, at the moment, salt is separated out, but a thick layer of calcium scale is formed at the position where liquid is in contact with the inner wall of the pipeline. Concentrating the solution in a double-effect evaporator to 55% sulfuric acid.
Comparative example 4 (changing pressure and temperature)
Titanium dioxide waste acid with the sulfuric acid concentration of 23 percent (the iron-titanium ratio is 0.28) is preheated and then introduced into a one-effect concentration system, the sulfuric acid concentration in the one-effect concentration system is kept at 38 percent, the temperature is 40 ℃, the pressure is controlled to be 0.006MPa, salt can be separated out at the moment, but in the continuous concentration process, salt is continuously separated out at the position where the liquid is contacted with the inner wall of the pipeline and is attached to the inner wall to form a layer of thick scale, and the scale is difficult to clean. Concentrating the solution in a double-effect evaporator to 55% sulfuric acid.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (6)
1. A method for preventing multi-effect concentration and one-effect scaling of titanium dioxide waste acid produced by a sulfuric acid process is characterized by comprising the following steps:
(1) directly introducing titanium white waste acid with the concentration of 20-30% into a primary-effect concentration system, adding concentrated sulfuric acid to keep the acid concentration in the primary-effect concentration system at 38-42%, wherein the temperature of the primary-effect concentration system is 103-106 ℃, the vacuum degree is 48-52 kpa, and the primary-effect concentration overflows into a secondary-effect concentration system after being in stable boiling;
(2) and (3) keeping the vacuum degree of the double-effect concentration system at 88-92 kpa, keeping the temperature at 76-78 ℃, enabling the concentrated sulfuric acid to reach the concentration of 53-55%, entering a curing tank, cooling and crystallizing, carrying out solid-liquid separation to remove impurities, and continuously concentrating or recycling the concentrated finished acid.
2. The method according to claim 1, wherein the iron-titanium ratio in the titanium liquid in the titanium white production process is 0.26-0.42.
3. The method according to claim 1, characterized in that the titanium dioxide spent acid has a concentration of 22-25%.
4. The method as claimed in claim 1, wherein the concentrated finished acid is added to the primary concentration system or the sulfuric acid is obtained by using secondary concentration overflow without separation from the viewpoint of energy saving.
5. The method of claim 1, wherein the concentration of sulfuric acid in the single effect concentration system is 38%, the temperature is 103 ℃, and the vacuum is 48 kpa.
6. The method of claim 1, wherein the temperature of the double effect concentration system is 76.5 ℃ and the vacuum degree is 88 kpa.
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