CN104211097A - Method for preparing lithium hydrogencarbonate solution - Google Patents

Abstract

The invention relates to the technical field of chemical industry separation and purification, in particular to a method for preparing a lithium hydrogencarbonate solution. The method includes the following steps that a lithium carbonate raw product is obtained and dissolved in distilled water to prepare lithium carbonate slurry with material concentration of 40-80g/L; the slurry enters a rotating packed bed, CO2 gases are fed into the rotating packed bed, and carbonization reaction is performed for 40-100 minutes to obtain a material liquid; the feeding speed of the slurry is controlled to be 100-400mL/min, and the rotating speed of the rotating packed bed is controlled to be 10-50Hz; the CO2 gas flow is controlled to be 0.02-0.15m3/L; the material liquid is subjected to solid-liquid separation to obtain the lithium hydrogencarbonate solution. According to the method for preparing the lithium hydrogencarbonate solution, a supergravity technology is combined, the high-speed rotating packed bed is used as a reaction device, compared with methods in the prior art, the method can greatly increase the converting efficiency of lithium carbonate to lithium hydrogencarbonate through adjustment of reaction conditions in the lithium carbonate carbonation process, and meanwhile, the reaction time can be shortened.

Description

A kind of preparation method of lithia water

Technical field

The present invention relates to chemical separation and purification technical field, relate in particular to a kind of carbonization method of Quilonum Retard.

Background technology

It is raw material that the thick product slip of Quilonum Retard is take in the preparation of pure Lithium Carbonate conventionally, by passing into wherein CO ₂there is carburizing reagent and obtain lithia water, then through ion exchange resin removal step, by pyrolytic reaction, make pure Lithium Carbonate product afterwards.Therefore, the preparation of lithia water is that preparation one of pure Lithium Carbonate must be through process.How to improve Crude lithium Carbonate to the transformation efficiency of lithium bicarbonate process, and to shorten this transformation time be to prepare one of the lithia water problem that must consider.

In the optimization of Dai Zhifeng carburizing reagent in the < < pure Lithium Carbonate preparation process of delivering for 2005 and the research > > Master degree candidate Diplomarbeit of calcium-magnesium removing, show: when carbonization temperature is at 20 ℃, the carburizing reagent time when 90min, CO ₂the unit time flow control of gas is at 2.667L/min (0.16m ³/ h) time, can make the speed of carburizing reagent reach maximum, carbonization most effective, the transformation efficiency of Quilonum Retard reaches 78.7%.Even if extend the reaction times during to 150min, the transformation efficiency of Quilonum Retard is only also 79.2%.

Chemical process intensifying technology refers to and can significantly reduce chemical industry equipment volume, reduction device quantity, and simplification of flowsheet, strengthening chemical process, the chemical industry new technology of energy-conserving and environment-protective, therefore meet society energy-saving and emission-reduction, environment amenable demand for development, is considered to solve the effective technology means of chemical industry " high energy consumption, high pollution and high material-consumption " problem.High-gravity technology is to have one of technology of development prospect in chemical process intensifying technology.It has equipment microminiaturization, efficiency is high, energy consumption is low, easy running, the safe and reliable and advantage such as suitability widely, therefore in fields such as chemical industry, material, biology and environmental protection, has broad application prospects.

The centrifugal force that high-gravity technology produces by high speed rotating just increases universal gravity constant, and simulation Elevated Gravity is realized the technology of strengthening microcosmic mixing and mass transfer process.The equipment of simulation Elevated Gravity is called high speed rotating bed of packings.Gas liquid reaction adopts adverse current high speed rotating bed of packings more, for example, its structure can be referring to Chen Jianfeng 2002 Chemical Industry Press, shown in the < < high-gravity technology of delivering and application > >.

People urgently wish high-gravity technology to be bonded to Quilonum Retard in the middle of the Transformation Application of lithium bicarbonate.

Summary of the invention

For overcoming the deficiencies in the prior art, the invention provides a kind of preparation method of lithia water, it comprises the steps:

Step 1: get the thick product of Quilonum Retard and be dissolved in and be mixed with the Quilonum Retard slip that material concentration is 40～80g/L in distilled water;

Step 2: make described slip enter rotary packed bed in, and pass into CO to described in rotary packed bed ₂gas, carries out obtaining feed liquid after the carburizing reagent of 40～100min; Wherein, the input speed of controlling described slip is 100～400mL/min, rotary packed bed rotating speed for not higher than 50Hz; And CO ₂gas flow is 0.02～0.15m ³/ L;

Step 3: described feed liquid is carried out to solid-liquid separation, obtain lithia water.

Further, described material concentration is 50～70g/L; Described CO ₂gas flow is 0.04～0.12m ³/ L; Described rotary packed bed rotating speed is 10～50Hz; Described feeding rate is 150～350mL/min.

Further, described material concentration is 50～60g/L; Described CO ₂gas flow is 0.08～0.12m ³/ h; Described rotary packed bed rotating speed is 30～50Hz; Described feeding rate is 250～350mL/min.

Further, the described carburizing reagent time is 50～90min.

Beneficial effect:

The present invention is in conjunction with high-gravity technology, adopts high speed rotating bed of packings as conversion unit, by adjusting the reaction conditions of Quilonum Retard carbonization process, than prior art, greatly improved the transformation efficiency that Quilonum Retard is converted into lithium bicarbonate, also shortened the reaction times simultaneously.Technique of the present invention is simple, and simple operation is conducive to batch production; Reaction times is short, and transformation efficiency is high, and the utilization of resources is efficient, has broad application prospects.

Accompanying drawing explanation

Fig. 1 (a)～(d) is the trend map of each influence factor of the present invention and transformation efficiency.

Fig. 2 (a)～(d) is each influence factor of the present invention and the trend map in reaction times.

Embodiment

Below, describe with reference to the accompanying drawings embodiments of the invention in detail.Yet, can implement in many different forms the present invention, and the present invention should not be interpreted as being limited to the specific embodiment of setting forth here.On the contrary, it is in order to explain principle of the present invention and practical application thereof that these embodiment are provided, thereby makes others skilled in the art can understand various embodiment of the present invention and be suitable for the various modifications that certain expected is applied.

It is raw material that the thick product slip of Quilonum Retard is take in the present invention, by high-gravity technology, prepares lithia water.By the investigation to material concentration, gas flow, high speed rotating bed of packings rotating speed, feeding rate, obtain the preparation method of lithia water rapidly and efficiently.

The present invention adopts and oldly builds adverse current high speed rotating bed of packings that peak provides as conversion unit, and during the work of adverse current high speed rotating bed of packings, extraneous liquid can, under peristaltic pump is assisted, enter rotor internal cavity from liquid-inlet.Under the effect of filler, circumferential speed increases, and the centrifugal force producing pushes it against rotor outer rim.Gas phase tangentially enters rotor outer rim through gas feed, under the effect of gaseous tension, enters in filler.Liquid in high dispersive, high turbulence, mix and interface more contacts so that great speed of relative movement is reverse with gas under news rapidly by force, has greatly been strengthened mass transfer process.Afterwards, liquid is thrown to shell by rotor and collects by liquid exit and discharge.Gas leaves rotor from rotor center, by pneumatic outlet, is drawn, and completes whole mass transfer or reaction process.

The concrete implementation step of the present invention is as follows:

Step 1: get the thick product m of Quilonum Retard _x1(purity is more than 99.5%) is dissolved in 1L distilled water, and stirring obtains having default material concentration, and (unit, the thick product slip of Quilonum Retard g/L), then pours in four-necked bottle, continues to stir.

Step 2: by peristaltic pump, described slip is sent in high speed rotating bed of packings, regulated high speed rotating bed of packings rotating speed, after flow rate of liquid and stabilization of speed, then pass into CO to described in rotary packed bed ₂gas, carries out carbonization to described slip.Wherein, control described slip input speed (unit, mL/min), rotary packed bed rotating speed (unit, Hz) and CO ₂the flow of gas (unit, m ³/ L) to preset range.

Wherein, in order accurately to judge reaction end, in whole carbonization process, preferably every 5 minutes, measure pH, until the variation range of pH is no more than 0.02, determine that this is reaction end constantly.Record whole reaction times t _x(min).

Step 3: after question response is complete, be converted into lithium bicarbonate feed liquid (abbreviation carbonization process) after the carbonization of described Quilonum Retard slip.Described feed liquid is analyzed, calculated the transformation efficiency of carbonization process.

Then the feed liquid obtaining after reacting completely is carried out to suction filtration, obtain filtrate and the filter cake of clarification.Wherein, after described filtrate sampling, carry out inductively coupled plasma atomic emission spectrum test, measure lithium concentration C in filtrate _x; Described filter cake is dried, weighs, and recording quality m _x2.

Last in conjunction with above-mentioned obtained data, according to the transformation efficiency ω of formula 1 calculating carbonization process _x(%).

${\mathrm{\&omega;}}_x=\frac{C_x\left({\mathrm{Li}}^{+}\right)\&times;V_x\&times;M\left({\mathrm{Li}}_2{\mathrm{CO}}_3\right)}{M\left({\mathrm{Li}}^{+}\right)\&times;2\&times;(m_{x1}-m_{x2})}$

Wherein, C _x(Li ⁺) be lithium concentration in filtrate, the g/L of unit;

V _xfor the material liquid volume obtaining after carburizing reagent, the L of unit;

M (Li ₂cO ₃) be the molar mass of Quilonum Retard, unit is g/mol;

M (Li ⁺) be the molar mass of lithium ion, unit is g/mol;

M _x1for the quality of Quilonum Retard crude product before carburizing reagent, unit is g;

M _x2for the quality of described filter cake after carburizing reagent, unit is g.

Particularly, in order to carry out four large influence factors of described carbonization process: material concentration (A), gas flow (B), rotary packed bed rotating speed (C), feeding rate (D) are analyzed the influence degree of technique, to finding out further more preferred implementation condition.The present invention is through a large amount of embodiment surface, by high-gravity technology under following implementation condition the transformation efficiency that obtains all higher than the carbonization process transformation efficiency of prior art:

Material concentration: 40～80g/L; Gas flow: 0.02～0.15m ³/ L; High speed rotating bed of packings rotating speed: 10～50Hz; Feeding rate: 100～400mL/min.

Wherein, for a step more, select better implementation condition, selecting several numerical points in the corresponding scope of ABCD, to be set to the preset value of embodiment as shown in table 1.

Each influence factor preset value of table 1ABCD

The present invention is provided with 9 embodiment, and the implementation condition of this embodiment 1～9 is as shown in table 2 respectively, and it is as shown in table 3 according to this implementation condition, to obtain respective reaction result.Choose transformation efficiency ω _xfor principal reaction index, carry out extreme difference R analysis, result is as shown in table 4.

Each embodiment reaction conditions of table 2

Embodiment	A(g/L)	B(m 3/h)	C(Hz)	D(mL/min)
					1	50	0.04	30	150
2	50	0.08	40	250
					3	50	0.12	50	350
4	60	0.04	40	350
					5	60	0.08	50	150
6	60	0.12	30	250

7	70	0.04	50	250
					8	70	0.08	30	350
9	70	0.12	40	150

Each embodiment reaction result of table 3

Embodiment	t x(min)	C x(g/L)	m x2(g)	ω x(％)
					1	102	7.233	6.9	90.2
2	68	8.155	3.9	94.1
					3	55	8.335	5.1	98.9
4	53	7.881	12.3	88
					5	73	7.773	14.2	90.3
6	58	7.929	14.3	92.4
					7	57	8.090	22.9	91.4
8	50	7.834	21.6	86
					9	87	7.065	25	83

Corresponding k (the ω of each influence factor of table 4 _x) value and R value

?	A(g/L)	B(m 3/h)	C(Hz)	D(mL/min)
					k 1(ω x)	94.400	89.867	89.533	87.833
k 2(ω x)	90.233	90.133	88.367	92.633
					k 3(ω x)	86.800	91.433	93.533	90.967
R	7.600	1.566	5.166	4.800

As shown in Table 3, under four kinds of default influence factor conditions, embodiment 1～9 just reacts completely in 50～102min, can obtain 83%～98.9% high transformation efficiency.Than the carburizing reagent 90～150min of prior art, obtain Quilonum Retard much higher less than 80% transformation efficiency.

Below, by range analysis, judge the affect primary and secondary of each influence factor on indicator reaction, with this, further obtain best implementation condition.Extreme difference R value is larger, represents that influence factor is larger on the impact of indicator reaction, and influence factor is more important; The impact of the influence factor that on the contrary, extreme difference R value is little is less.In comparison sheet 4, each R value size, finds that R value is R from big to small successively _a> R _c> R _d> R _b, what test transformation efficiency is had the greatest impact is material concentration, is secondly rotating speed and feeding rate, that impact is minimum is CO ₂gas flow.

Take each influence factor level is X-coordinate, and the mean value of indicator reaction is ordinate zou, draws influence factor and indicator reaction trend map.As shown in Fig. 1 (a), Fig. 1 (b), Fig. 1 (c), Fig. 1 (d).By influence factor and indicator reaction trend map, can be found out more intuitively the trend that test index changes along with the variation of influence factor level.Therefore can judge: when with transformation efficiency ω _xduring main experimental results, excellent level is A ₁, B ₃, C ₃, D ₂; The excellent A that is combined as ₁b ₃c ₃d ₂; Be material concentration 50g/L, CO ₂gas flow 0.12m ³/ h, high speed rotating bed of packings rotating speed 50Hz, feeding rate 250mL/min is the optimum process conditional combination of experiment.

If choose t _xfor main result, carry out range analysis, result is as shown in table 5.

Corresponding k (the t of each influence factor of table 5 _x) value and R value

?	A(g/L)	B(m 3/h)	C(Hz)	D(mL/min)
					k 1(t x)	75.000	70.667	70.000	87.333
k 2(t x)	61.333	63.667	69.333	61.000
					k 3(t x)	64.667	66.667	61.667	52.667
R	13.667	7.000	8.333	34.666

In comparison sheet 5, each R value size, finds that R value is R from big to small successively _d> R _a> R _c> R _b, what the reaction times is had the greatest impact is feeding rate, and impact is particularly remarkable compared with other influences factor.Next is material concentration and rotating speed, and that impact is minimum is CO ₂gas flow.

Take each influence factor level is X-coordinate, and the mean value of test index is ordinate zou, draws influence factor and index sign trend.As shown in Fig. 2 (a), Fig. 2 (b), Fig. 2 (c), Fig. 2 (d).By influence factor and index sign trend, can be found out more intuitively the trend that test index changes along with the variation of influence factor level.Hence one can see that, when with t _xfor main result can be chosen: excellent level is A ₂, B ₂, C ₃, D ₃, the excellent A that is combined as ₂b ₂c ₃d ₃, i.e. material concentration 60g/L, gas flow 0.08m ³/ h, high speed rotating bed of packings rotating speed 50Hz, feeding rate 350mL/min is the optimum process conditional combination of experiment.

With ω _xand t _xfor indicator reaction, analyze preferably span of each influence factor.

For influence factor A, analyze shown in associative list 6: if choose ω _xfor the excellent level of principal reaction index is chosen A ₁if choose t _xfor the excellent level of principal reaction index is chosen A ₂, i.e. the desirable A of the preferable range of material concentration A ₁～A ₂between.

For influence factor B, analyze shown in associative list 6: if choose ω _xfor the excellent level of principal reaction index is chosen B ₃if choose t _xfor the excellent level of principal reaction index is chosen B ₂, i.e. the desirable B of the preferable range of gas flow B ₂～B ₃between.

For influence factor C, analyze shown in associative list 6: if choose ω _xfor the excellent level of principal reaction index is chosen C ₃if choose t _xfor the excellent level of principal reaction index is chosen C equally ₃, the implementation condition of bed of packings rotating speed C the best is C ₃, but can not limit thus only this value of bed of packings rotating speed C, in the cited embodiment 1～9 of the present invention, bed of packings rotating speed is from C ₁～C ₃span all can realize the object of the invention.

For influence factor D, analyze shown in associative list 6: if choose ω _xfor the excellent level of principal reaction index is chosen D ₂if choose t _xfor the excellent level of principal reaction index is chosen D ₃, i.e. the desirable D of the preferable range of input speed D ₂～D ₃between.

The Comprehensive Correlation of each influence factor of table 6 on the impact of differential responses index

?	A(g/L)	B(m 3/h)	C(Hz)	D(mL/min)
					k 1(ω x)	94.400	89.867	89.533	87.833
k 2(ω x)	90.233	90.133	88.367	92.633
					k 3(ω x)	86.800	91.433	93.533	90.967
k 1(t x)	75.000	70.667	70.000	87.333
					k 2(t x)	61.333	63.667	69.333	61.000
k 3(t x)	64.667	66.667	61.667	52.667

Can show that controlling each factor of influence resulting transformation efficiency in suitable scope will be the selection of further optimizing, i.e. material concentration 50～60g/L, gas flow 0.08～0.12m ³/ h, high speed rotating bed of packings rotating speed 30～50Hz, feeding rate 250～350mL/min is the most preferred processing condition of the present invention.

Although exemplified and described the present invention with reference to particular implementation, but it should be appreciated by those skilled in the art that: in the situation that do not depart from the spirit and scope of the present invention that limited by claim and equivalent thereof, can carry out the various variations in form and details at this.

Claims (4)

1. a preparation method for lithia water, is characterized in that, comprises the steps:

Step 1: get the thick product of Quilonum Retard and be dissolved in and be mixed with the Quilonum Retard slip that material concentration is 40～80g/L in distilled water;

Step 2: make described slip enter rotary packed bed in, and pass into CO to described in rotary packed bed ₂gas, carries out obtaining feed liquid after the carburizing reagent of 40～100min; Wherein, the input speed of controlling described slip is 100～400mL/min, rotary packed bed rotating speed for not higher than 50Hz; And CO ₂gas flow is 0.02～0.15m ³/ L;

Step 3: described feed liquid is carried out to solid-liquid separation, obtain lithia water.

2. the preparation method of lithia water according to claim 1, is characterized in that, described material concentration is 50～70g/L; Described CO ₂gas flow is 0.04～0.12m ³/ L; Described rotary packed bed rotating speed is 10～50Hz; Described feeding rate is 150～350mL/min.

3. the preparation method of lithia water according to claim 2, is characterized in that, described material concentration is 50～60g/L; Described CO ₂gas flow is 0.08～0.12m ³/ h; Described rotary packed bed rotating speed is 30～50Hz; Described feeding rate is 250～350mL/min.

4. the preparation method of lithia water according to claim 1, is characterized in that, the described carburizing reagent time is 50～90min.