阅读说明：本技术 一种石墨强化的水合物法锂离子连续富集系统及方法 (A kind of continuous enrichment system of hydrate lithium ion and method of graphite reinforcing ) 是由 宋永臣 凌铮 李峰 石常瑞 杨雅梅 周航 赵佳飞 李洋辉 杨明军 于 2019-08-13 设计创作，主要内容包括：一种石墨强化的水合物法锂离子连续富集系统,属于水合物技术应用领域。该连续富集系统包括水合物生成系统、水合物分解系统、电导率实时测量系统、锂溶液循环系统和环戊烷循环系统。本发明适用于盐湖卤水及海水中高附加值金属锂离子的富集,通过环戊烷水合物在常压低温下生成对盐的排除效应,利用反应锂盐溶液的循环以及水合物的连续生成过程,实现了锂离子的连续富集,同时对反应后盐溶液的在线电导率监测可以实现对锂离子富集程度的实时观察。该系统具有较好的连续性及普适性,能够对不同的锂盐溶液进行富集,同时水合物的分解能够生产出淡水,实现了资源的合理化利用。(A kind of continuous enrichment system of hydrate lithium ion that graphite is strengthened, belongs to Hydrate Technology application field.The continuous enrichment system includes that hydrate generates system, decomposition of hydrate system, conductivity real-time measurement system, lithium solution recycle system and the pentamethylene circulatory system.The enrichment of present invention high added value metal-lithium ion suitable for salt lake bittern and seawater, the exclusion effect to salt is generated under atmospheric low-temperature by pentamethylene hydrate, process is continuously generated using the circulation and hydrate for reacting lithium salt solution, the continuous enrichment of lithium ion is realized, while the real-time observation to lithium ion enrichment degree may be implemented to the online monitored conductivity of salting liquid after reaction.The system has preferable continuity and universality, can be enriched with, while the decomposition of hydrate can produce fresh water to different lithium salt solutions, realize the rational utilization of resource.)

1. the continuous enrichment system of hydrate lithium ion that a kind of graphite is strengthened, which is characterized in that including hydrate generate system, Decomposition of hydrate system, conductivity real-time measurement system, lithium solution recycle system and the pentamethylene circulatory system；

It includes hydrate reaction kettle and cycle refrigeration system that the hydrate, which generates system,；The hydrate reaction kettle (37) is by stone English glass is made, and is used for process visualization, and internal layer loads the reaction that graphite (36) are used for hydrate, and outer layer is passed through coolant liquid (35) it is controlled for temperature, bottom is used to obstruct the circulation that solid carries out liquid equipped with filter core (38)；The cycle refrigeration system It is interior to be equipped with heating and refrigeration system for heating/refrigerating circulator bath (14), temperature control is carried out by built-in temperature sensor；

The decomposition of hydrate system includes fresh water collecting device and recycling graphite recycling system；The fresh water collecting device For carrying out the collection storage of production fresh water after decomposition of hydrate；The recycling graphite recycling system is after decomposition of hydrate The recycling that graphite is carried out by solid-liquid separator, is stored in graphite storage tank (32), and when use is transported to by delivery pump In reaction kettle；

The conductivity real-time measurement system includes conductivity meter and computer acquisition equipment (23)；The conductivity meter (22) is used The real-time conductivity of solution after measurement concentration, and its data is transmitted to computer acquisition equipment；The computer acquisition is set It is ready for use on the real-time conductivity data for receiving conductivity meter transmission and is recorded and analyzed；

The lithium solution recycle system includes the first centrifugal pump (2), first heat exchanger (3), lithium solution circulating tank (1) and first Flowmeter (5)；The lithium solution being concentrated after reaction reacts in first heat exchanger (3) with entrance after passing through fluid separator (19) Lithium solution before kettle carries out heat exchange, cools down in advance to the solution of reaction, and the flow of lithium solution is controlled by flowmeter；

The pentamethylene circulatory system includes the second centrifugal pump (7), second heat exchanger (8), pentamethylene circulating tank (6) and second Flowmeter (10)；The pentamethylene of reaction is not participated in by second heat exchanger (8) and entering anti-after fluid separator (19) Pentamethylene before answering kettle carries out heat exchange, cools down in advance to the pentamethylene of reaction, and is controlled by second flowmeter (10) The flow of pentamethylene.

2. the continuous enrichment system method of hydrate lithium ion that graphite described in claim 1 is strengthened, which is characterized in that step It is as follows:

Step 1: opening cycle refrigeration system (14), temperature is set, is controlled by third globe valve (15) and the 4th globe valve (16) The refrigeration flow quantity of system disengaging autoclave body, is allowed to reach balance；

Step 2: passing through the first centrifugal pump (2) and the second centrifugal pump (7) will contain lithium salt solution respectively and pentamethylene is transported to kettle It is interior, lithium liquid inventory and pentamethylene flow reading are read according to first flowmeter (5) and second flowmeter (10) respectively, utilize One globe valve (4) and the second globe valve (9) control the flow of lithium solution and the flow of pentamethylene respectively, are allowed to reach required match Than；Mixed liquor is atomized after mixing valve (11) mix by sprayer (13) by lithium solution and pentamethylene, subsequently into reaction kettle (37) in；

Step 3: hydrate is generated using graphite (36) as in the reaction kettle (37) of promotor, open gate valve (17), utilizes Unreacted lithium-containing solution and pentamethylene are entered fluid separator (19) by filter core (38) by the first rotary pump (18), and are given birth to At hydrate solids be left in reaction kettle (37)；

Step 4: being separated lithium-containing solution and pentamethylene by fluid separator (19), pentamethylene passes through the second delivery pump (24) It enters second heat exchanger (8) to exchange with the pentamethylene progress heat that will go into reaction kettle (37), is then return to ring Pentane circulating tank (6) is recycled；Conductivity inspection is carried out to the lithium-containing solution in cyclic process using conductivity meter (22) It surveys, and passes through computer acquisition equipment (23) record storage detection data；Then lithium-containing solution is returned by first heat exchanger (3) Into lithium solution circulating tank；Whole process constantly recycles, with hydrate production quantity increase cyclic process in lithium solution it is dense Degree is continuously increased；

Stop step 5: being recycled when the lithium solution concentration for detecting cyclic process reaches requirement, the lithium-containing solution being enriched with； It closes the first globe valve (4), the second globe valve (9) and the first gate valve (17) at this time, opens the second gate valve (26), allow the water of generation It closes object and is decomposed by the second rotary pump (27) into decomposition of hydrate device (28)；Third gate valve is opened after decomposing completely (29) it allows decomposition product to enter solid-liquid separator (30) to be separated by solid-liquid separation, obtained fresh water solution storage to fresh water storage tank (31), graphite particle is recovered to graphite storage tank (32) and is recycled.

Technical field

The invention belongs to Hydrate Technology application field, the hydrate lithium ion for being related to a kind of graphite reinforcing is continuously enriched with System.

Background introduction

Lithium is the most light metal of nature, specific heat with higher and conductivity, a few days ago lithium ion be mainly used for glass and Ceramic industry, but with the continuous development of science and technology with progress, lithium and its compound using more and more extensive, demand Also increasing, the development of especially green electronic energy automobile, the demand of lithium ion is also year by year in production lithium battery Growth, this make future how to keep being supplied in for new challenge to lithium ion steadily.Lithium resource in nature Major storage in Granitic Ore Deposits and salt lake bittern, seawater, and the whole world salt lake bittern and seawater in lithium resource content compared with Height accounts for the 66% of world's lithium reserves, but to extract lithium resource also not a duck soup directly from brine and seawater.At present from sea The method for extracting lithium in water and salt lake mainly has ion exchange adsorption, solvent extraction and precipitation method etc..Ion-exchange absorption The molten loss rate of the adsorbent of attached method is quite high, and mobility and permeability are very poor, is difficult to be proposed lithium technology realization industrialization；Solvent extraction The complex process followed the example of, brine amount to be treated is big in extraction process, and energy consumption is high, severe corrosion to equipment, is easy to ring Border pollutes；The precipitation method are will to contain lithium brine natural evaporation concentration using solar energy, and the period of process is longer, are not utilized fast The lithium resource of speed extracts.That in short, existing tradition proposes lithium technology, there is energy consumptions is high, strong to equipment corrosion, the production cycle is long Etc. some column shortcomings.Therefore, finding the novel economy of one kind, environmental protection, quickly proposing lithium technology is that the following solution proposes lithium mistake Energy consumption problem and key the problems such as environmental pollution in journey.

Summary of the invention

Described above in order to solve the problems, such as, the hydrate lithium ion that the present invention provides a kind of graphite reinforcing, which is continuously enriched with, is System.The principle of the invention lies in the saluretic effects during utilization gas hydrate synthesis cagelike structure, by solution in successive reaction mistake Journey is constantly concentrated the enrichment to realize lithium ion, at the same using graphite have high specific surface area and good thermal conductivity as The inducer of hydrate nucleation, realizes quickly generating for lithium enrichment process hydrate, and graphite is easy to be separated from water, can be right Graphite after reaction is recycled to economize on resources, and has good economy.

The technical solution adopted by the present invention:

A kind of continuous enrichment system of hydrate lithium ion that graphite is strengthened, including hydrate generate system, hydrate point Solution system, conductivity real-time measurement system, lithium solution recycle system and the pentamethylene circulatory system；

It includes reaction kettle and temperature control system that the hydrate, which generates system,；The reaction kettle is made of quartz glass, The visualization of experimentation can be carried out, internal layer loads the reaction that graphite is used for hydrate, and outer layer is passed through coolant liquid for testing temperature The control of degree, bottom are used to obstruct the circulation that solid carries out liquid equipped with filter core；The temperature control system is followed for heating/refrigerating Ring water-bath, it is interior to be equipped with heating and refrigeration system, temperature control is carried out by built-in temperature sensor.

The decomposition of hydrate system includes fresh water collecting device and recycling graphite recycling system；The fresh water collecting Device is for carrying out the collection storage of production fresh water after decomposition of hydrate；The recycling graphite recycling system is in hydrate point The recycling for carrying out graphite after solution by solid-liquid separator, is stored in graphite storage tank, and when use is transported to by delivery pump In reaction kettle.

The conductivity real-time measurement system includes conductivity meter and computer acquisition equipment；The conductivity meter is for surveying The real-time conductivity of solution after amount concentration, and its data is transmitted to computer equipment；The computer acquisition equipment is for connecing It receives the real-time conductivity data of conductivity meter transmission and is recorded and analyzed.

The lithium solution recycle system includes fluid separator, heat exchanger, lithium solution circulating tank and flowmeter；After reaction The lithium solution of concentration is exchanged with into the lithium solution progress heat before reaction kettle in a heat exchanger after passing through fluid separator, right The solution of reaction cools down in advance, and the flow of lithium solution is controlled by flowmeter.

The pentamethylene circulatory system includes fluid separator, heat exchanger, pentamethylene circulating tank and flowmeter；It does not participate in The pentamethylene of reaction is exchanged with into the pentamethylene progress heat before reaction kettle in a heat exchanger after passing through fluid separator, right The pentamethylene of reaction cools down in advance, and the flow of pentamethylene is controlled by flowmeter.

The continuous enrichment system of hydrate lithium ion that a kind of graphite of the invention is strengthened utilizes following for reaction lithium salt solution Ring and hydrate continuously generate process, realize the continuous enrichment of lithium ion, while to the online electricity of salting liquid after reaction The real-time observation to lithium ion enrichment degree may be implemented in conductance monitoring.Promotor of the graphite as hydrate reaction process, In It can be recycled after decomposition of hydrate, with save the cost.The system has preferable continuity and universality, can be right Different lithium salt solutions are enriched with, while the decomposition of hydrate can produce fresh water, realize the rational utilization of resource. The present invention has many advantages, such as that energy conservation and environmental protection, equipment are simple, resource utilization is high.

Detailed description of the invention

Fig. 1 is a kind of continuous enrichment system figure of hydrate lithium ion that graphite is strengthened.

Fig. 2 is hydrate reaction device figure.

In figure: 1 lithium solution circulating tank；2 first centrifugal pumps；3 first heat exchangers；4 first globe valves；5 first flowmeters； 6 pentamethylene circulating tanks；7 second centrifugal pumps；8 second heat exchangers；9 second globe valves；10 second flowmeters；11 mixing valves；12 Check-valves；13 sprayers；14 heating/refrigerating circulator baths；15 third globe valves；16 the 4th globe valves；17 first gate valves；18 One rotary pump；19 fluid separators；20 first delivery pumps；21 first check-valves；22 conductivity meters；23 computer acquisition equipment； 24 second delivery pumps；25 second check-valves；26 second gate valves；27 second rotary pumps；28 decomposition of hydrate devices；29 third gate valves； 30 solid-liquid separators；31 fresh water storage tanks；32 graphite storage tanks；33 third delivery pumps；34 the 4th gate valves；35 coolant liquids；36 graphite；37 Hydrate reaction kettle；38 filter cores.

Specific embodiment

As shown, the continuous enrichment system of hydrate lithium ion that a kind of graphite of the invention is strengthened, including hydrate Generation system, decomposition of hydrate system, conductivity real-time measurement system, lithium solution recycle system and the pentamethylene circulatory system；

It includes hydrate reaction kettle and cycle refrigeration system that the hydrate, which generates system,；The hydrate reaction kettle 37 by Quartz glass is made, and is used for process visualization, and internal layer loads the reaction that graphite is used for hydrate, and outer layer is passed through coolant liquid and is used for Temperature control, bottom are used to obstruct the circulation that solid carries out liquid equipped with filter core 39；The cycle refrigeration system is heating/refrigerating Circulator bath 14, it is interior to be equipped with heating and refrigeration system, temperature control is carried out by built-in temperature sensor；

The decomposition of hydrate system includes fresh water collecting device and recycling graphite recycling system；The fresh water collecting Device is for carrying out the collection storage of production fresh water after decomposition of hydrate；The recycling graphite recycling system is in hydrate point The recycling for carrying out graphite after solution by solid-liquid separator 30, is stored in graphite storage tank 32, by delivery pump that its is defeated when use It send to reaction kettle.

The conductivity real-time measurement system includes conductivity meter 22 and computer acquisition equipment；The conductivity meter 22 is used The real-time conductivity of solution after measurement concentration, and its data is transmitted to computer acquisition equipment；The computer acquisition is set It is ready for use on the real-time conductivity data for receiving conductivity meter transmission and is recorded and analyzed.

The lithium solution recycle system includes the first centrifugal pump 2, first heat exchanger 3, lithium solution circulating tank 1 and first-class Meter 5；The lithium solution being concentrated after reaction pass through fluid separator after in first heat exchanger 3 with enter reaction kettle before lithium it is molten Liquid carries out heat exchange, cools down in advance to the solution of reaction, and the flow of lithium solution is controlled by flowmeter.

The pentamethylene circulatory system includes the second centrifugal pump 7, second heat exchanger 8, pentamethylene circulating tank 6 and second Meter 10；Do not participate in the pentamethylene of reaction by after fluid separator in a heat exchanger with enter the pentamethylene before reaction kettle into The exchange of row heat, cools down the pentamethylene of reaction in advance, and the flow of pentamethylene is controlled by flowmeter.

Using the method for the continuous enrichment system of hydrate lithium ion that above-mentioned graphite is strengthened, steps are as follows:

Temperature setting to experimental temperature is passed through into third globe valve 15 and the 4th step 1: opening cycle refrigeration system 14 The refrigeration flow quantity of the control disengaging autoclave body of globe valve 16, is allowed to reach balance；

Step 2: passing through the first centrifugal pump 2 and the second centrifugal pump 7 will contain lithium salt solution respectively and pentamethylene is transported to kettle It is interior, it is read according to lithium solution first flowmeter 5 and pentamethylene second flowmeter 10, utilizes the first globe valve 4 and the second globe valve 9 The flow of lithium solution and the flow of pentamethylene are controlled respectively, are allowed to proportion needed for reaching experiment；Lithium solution and pentamethylene are mixed It closes after valve 11 mixes and is atomized mixed liquor by sprayer 13, subsequently into hydrate reaction kettle 37；

Step 3: hydrate is generated in using hydrate reaction kettle 37 of the graphite 36 as promotor, the first lock is opened Unreacted lithium-containing solution and pentamethylene are entered fluid separator 19 by filter core 38 using the first rotary pump 18 by valve 17, And the hydrate solids generated are left in hydrate reaction kettle 37；

Step 4: being separated lithium-containing solution and pentamethylene by fluid separator 19, pentamethylene is entered by delivery pump 24 Heat is carried out with the pentamethylene that will go into reaction kettle 37 to second heat exchanger 8 to exchange, and is then return to pentamethylene circulation Tank 6 is recycled；Conductivity detection is carried out to the lithium-containing solution in cyclic process using conductivity meter 22, and passes through calculating 23 record storage detection data of machine, then lithium-containing solution returns in lithium solution circulating tank by first heat exchanger 3；Whole process Constantly circulation, as the concentration of lithium solution in the increase cyclic process of hydrate production quantity is continuously increased；

Stop step 5: being recycled when the lithium solution concentration for detecting cyclic process reaches requirement of experiment, is enriched with Lithium-containing solution；It closes the first globe valve 4, the second globe valve 9 and the first gate valve 17 at this time, opens the second gate valve 26, allow generation Hydrate is decomposed by the second rotary pump 27 into decomposition of hydrate device 28；Third gate valve 29 is opened after decomposing completely to allow Decomposition product enters solid-liquid separator 30 and is separated by solid-liquid separation, obtained fresh water solution storage to fresh water storage tank 31, graphite particle Graphite storage tank 32 is recovered to be recycled.