CN101857204A - Process and device for purifying sulfuric acid phase in iodine and sulfur cycle under low pressure - Google Patents
Process and device for purifying sulfuric acid phase in iodine and sulfur cycle under low pressure Download PDFInfo
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Abstract
The invention relates to a process and a device for purifying a sulfuric acid phase in the iodine and sulfur cycle under low pressure and belongs to the technical field of hydrogen production of the iodine and sulfur thermochemical cycle. The process for purifying the sulfuric acid phase is carried out under the condition of lower than normal pressure, i.e. under the condition of a purification temperature between 50 and 200 DEG C, a pressure P of a purifying and concentrating tower is controlled in the range that P is more than or equal to 0.01atm and less than 1atm. Compared with the conventional sulfuric acid phase purification process which adopts a nitrogen purging mode under normal pressure, the process has the characteristics of low purification temperature, simple process and low cost and can realize purification and concentration of the sulfuric acid phase in one step so as to effectively improve the purifying efficiency and reduce the purifying and concentrating cost.
Description
Technical field
The present invention relates under a kind of low pressure the technology and the device of sulfuric acid phase in the sulphur cycle of purifying iodine, belong to the thermochemical cycle for hydrogen production correlative technology field.
Background technology
Energy system based on fossil oil serves as to promote human social development to make huge contribution.Yet the fossil oil reserves are limited, non-renewable, can cause environmental pollution in the use.Because hydrogen has the calorific value height, has good burning performance, renewable and clean advantages such as nontoxic, so Hydrogen Energy is considered to human future source of energy.The active development Hydrogen Energy is becoming the energy strategy of many countries.Yet traditional hydrogen production process exist some shortcomings that self are difficult to overcome as: utilize fossil oil to prepare hydrogen and have CO
2Emission problem, water electrolysis hydrogen producing efficient is low, the hydrogen manufacturing cost is more high.Therefore research and development cleaning, efficient, large-scale hydrogen production process more and more are subject to people's attention.The hydrogen production process of bibliographical information comprises the decomposition of water direct heat, thermochemical cycle water of decomposition, high-temperature electrolysis, sun power photodissociation water, biomass hydrogen preparation etc., and wherein the thermochemical cycle hydrogen production by water decomposition is one of very promising method.And in numerous thermochemical cycle, iodine sulphur (IS) circulation of U.S. GA company invention is chosen to be the first-selected flow process of following nuclear energy hydrogen manufacturing by many countries such as the U.S., Japan, France.This process is made up of 3 reactions:
(1) Bunsen reaction (heat release ,～120 ℃): SO
2+ I
2+ 2H
2O=2HI+H
2SO
4
(2) sulfuric acid decomposes (heat absorption, 800-900 ℃): H
2SO
4=H
2O+SO
2+ 1/2O
2
(3) hydrogen iodide decomposes (heat absorption, 300-500 ℃): 2HI=H
2+ I
2
The chemical reaction that above-mentioned three heat drive is coupled, and forms a closed cycle, and clean reaction is water decomposition: H
2O=H
2+ 1/2O
2We can say that in whole process except consume water, other all materials all recycle.The water decomposition that the iodine sulphur cycle will need to carry out under the high temperature more than 2500 ℃ is originally reacted, and is achieved under 800～900 ℃, and CO is easily carried, do not had to hydrogen generation efficiency height, reaction mass
2Discharging, above-mentioned advantage makes the iodine sulphur cycle be expected to become cleaning, economy, continuable extensive hydrogen production process.
, though the IS circulation theory is simple, really realize the industrialization hydrogen manufacturing of iodine sulphur cycle, the problem of many science and technologies aspect all will solve.Wherein the purifying of one of Benson (Bunsen) reaction product sulfuric acid phase is exactly a problem that needs solution.Under the higher reaction conditions of iodine concentration, two kinds of acid that Benson reaction generates can spontaneously be divided into two-phase: light liquid phase sulfuric acid mutually with heavy-fluid hydroiodic acid HI phase mutually.The existence of partition equilibrium makes unavoidably and contains a small amount of hydroiodic acid HI during sulfuric acid is mutually that these a spot of hydroiodic acid HI impurity tend to sulfuric acid following side reaction take place:
(4) S formation reaction: H
2SO
4+ 6HI=S+3I
2+ 4H
2O
(5) H
2S formation reaction: H
2SO
4+ 8HI=H
2S+4I
2+ 4H
2O
The generation of side reaction results in hand cramps for the operation of iodine sulphur cycle, and as destroying material balance, the generation meeting blocking pipe of solid-state sulphur hinders mass transport, reduces hydrogen production efficiency, thereby influences the normal operation of closed cycle.Therefore must carry out purifying mutually to sulfuric acid, eliminate sulfuric acid mutually in a spot of hydroiodic acid HI.
From present disclosed document and technical information, the principle that many countries carry out sulfuric acid phase purifying all is the reversed reaction of Benson reaction: (6) 2HI+H
2SO
4=SO
2+ I
2+ 2H
2O.In the iodine sulphur cycle research of Japan, Korea S and China, reference " Kubo S; Nakajima H; Kasahara S, Higashi S, Masaki T; Abe H; Onuki K.Ademonstration study on a closed-cycle hydrogen production by the thermochemicalwater-splitting iodine-sulfur process.Nucl.Eng.Des., 2004,233:347-354 " for example; " Ki-Kwang Bae; Chu-Sik Park; Chang-Hee Kim; Kyung-Soo Kang; Sang-Ho Lee; Gab-Jin Hwang, Ho-Sang Choi.Hydrogen production by thermochemical water-splitting IS process.WHEC 16/13～16 June 2006-Lyon France "; " Guo H F, Zhang P, Bai Y, Wang L J, Chen S Z, Xu J M, Continuous purification of H
2SO
4AndHI phases by packed column in IS process, Int.J.Hydrogen Energy.35 (7) (2010) 2836-2839 "; sulfuric acid phase purifying process is basic identical; all adopt under the normal pressure nitrogen to make sweep gas; impel the reversed reaction of Benson reaction to take place under the heating condition, remove sulfuric acid mutually in a spot of hydroiodic acid HI.There is following shortcoming in this purifying process: (i) use of nitrogen has increased material cost, makes the iodine sulphur cycle become the nitrogen cycle of iodine sulphur to a certain extent; The (ii) use of nitrogen need hold the steel cylinder of nitrogen, reducing valve, the flow instrument of dominant discharge and the pipeline of supplying nitrogen of adjusting pressure, and this can increase equipment cost; (iii) nitrogen introducing iodine sulphur cycle system finally must separate from system, and this just needs to increase separating technology, thereby increases the complicacy of technology.And the purifying of sulfuric acid phase carries out separately on purifying and concentrating unit respectively with concentrated, and the technology cost is higher.
Summary of the invention
In order to solve the issues of purification of sulfuric acid phase in the iodine sulphur cycle, overcome traditional normal pressure nitrogen purging purifying process and have starting material and shortcomings such as equipment cost is higher, complex process, the invention provides under a kind of low pressure the technology and the device of sulfuric acid phase in the sulphur cycle of purifying iodine.
Concrete technical scheme of the present invention is as follows:
The processing method of sulfuric acid phase in the sulphur cycle of purifying iodine is characterized in that this method comprises the steps: under a kind of low pressure
1) is controlled to be 0.01atm≤P＜1atm at first with purifying upgrading tower heat temperature raising to 50～200 ℃, and with purifying upgrading tower pressure P; By the liquid flow rate control pump sulfuric acid of known component is imported from purifying upgrading tower top opening for feed then;
2) in the purifying upgrading tower, the hydroiodic acid HI of sulfuric acid in mutually and the reversed reaction of part of sulfuric acid generation Benson reaction: H
2SO
4+ 2HI=SO
2+ I
2+ 2H
2The SO that O, purification reaction obtain
2, I
2And H
2O extracts and is delivered to the Benson reactor out from purifying upgrading tower upper end venting port;
3) sulfuric acid that is purified flows out from the liquid outlet opening of purifying upgrading tower lower end.
The device of sulfuric acid phase in the sulphur cycle of purifying iodine under a kind of low pressure provided by the invention, it is characterized in that: the refined solution storage tank that described device comprises stock liquid storage tank, purifying upgrading tower, vacuum control valve, process furnace, temperature controller and is arranged on purifying upgrading tower bottom, described stock liquid storage tank is connected with purifying upgrading tower top opening for feed by the pipeline that liquid flow rate adjusting pump is housed; Described vacuum control valve is connected with the venting port at purifying upgrading tower top by the venting port stopping valve; Described refined solution storage tank is connected by the liquid outlet opening of leakage fluid dram stopping valve with purifying upgrading tower bottom.
The present invention compared with prior art, have the following advantages and the high-lighting technique effect: adopt low pressure purifying process of the present invention and low pressure purification devices to come sulfuric acid in the iodine sulphur cycle is carried out purifying mutually, compare with the two-phase purifying process under traditional normal pressure nitrogen purging, cancelled the use of nitrogen, overcome because of using the shortcoming of starting material that nitrogen brings and equipment cost height, complex process etc., and the purifying for the sulfuric acid phase can be realized in a step with concentrated, cleansing temp is lower, can improve purification efficiency, reduce the purifying concentrated cost.
Description of drawings
Fig. 1 is a sulfuric acid phase purifying process device synoptic diagram.
Among Fig. 1: 1-stock liquid storage tank; The 2-liquid flow rate is regulated pump; 3-purifying upgrading tower; 4-venting port stopping valve; The 5-vacuum control valve; The 6-tensimeter; The 7-process furnace; The 8-temperature controller; 9-leakage fluid dram stopping valve; 10-refined solution storage tank.
Fig. 2 is that the change of 110 ℃ of overdraft is to H in HI transformation efficiency, the refined solution
2SO
4Mass percent concentration, SO
2Optionally influence with S.
Fig. 3 is that the change of 110 ℃ of overdraft is to product S O
2And I
2The influence of partition ratio in each phase.
Fig. 4 is that the change of 60 ℃ of overdraft is to H in HI transformation efficiency, the refined solution
2SO
4Mass percent concentration, SO
2Optionally influence with S.
Fig. 5 is that the change of 60 ℃ of overdraft is to product S O
2And I
2The influence of partition ratio in each phase.
Fig. 6 changes temperature down to H in HI transformation efficiency, the refined solution for 0.06atm
2SO
4Mass percent concentration, SO
2Optionally influence with S.
Embodiment
Describe the present invention in detail below in conjunction with drawings and Examples.
Fig. 1 is a sulfuric acid phase purifying process device synoptic diagram, and this device comprises stock liquid storage tank 1, liquid flow rate adjusting pump 2, purifying upgrading tower 3, venting port stopping valve 4, vacuum control valve 5, tensimeter 6, process furnace 7, temperature controller 8,9 leakage fluid dram stopping valve and refined solution storage tank 10.Stock liquid storage tank 1 is connected with purifying upgrading tower 3 top opening for feeds by the pipeline that liquid flow rate adjusting pump 2 is housed; Vacuum control valve 5 is connected with the venting port at purifying upgrading tower top by venting port stopping valve 4, top at purifying upgrading tower 3 also is connected with tensimeter 6, the temperature of purifying upgrading tower 3 is by process furnace 7 and temperature controller 8 controls, in the bottom of purifying upgrading tower 3 leakage fluid dram stopping valve 9 is housed, this leakage fluid dram stopping valve links to each other with refined solution storage tank 10.
It is as follows to adopt said apparatus sulfuric acid in the iodine sulphur cycle to be carried out mutually the step of technology of purifying:
At first with purifying upgrading tower 3 heat temperature raisings to 50～200 ℃, and utilize the temperature of process furnace 7 and temperature controller 8 control purifying upgrading towers, utilize vacuum control valve 5 that purifying upgrading tower system pressure P is controlled to be: 0.01atm≤P＜1atm; Regulating pump 2 by liquid flow rate imports from stock liquid storage tank 1 sulfuric acid of known component via purifying upgrading tower top opening for feed.Flow through the mutually purifying upgrading tower of temperature control and low pressure of sulfuric acid, sulfuric acid a small amount of hydroiodic acid HI and the reversed reaction of part of sulfuric acid generation Benson reaction: the H in mutually
2SO
4+ 2HI=SO
2+ I
2+ 2H
2The SO that O, purification reaction obtain
2, I
2And H
2O is extracted out and is delivered to the Benson reactor from purifying upgrading tower upper end venting port by vacuum control valve 5, thereby reaches the purpose of purification of sulphuric acids phase.The sulfuric acid of purifying flows into sulfuric acid phase refined solution storage tank 10 from purifying upgrading tower bottom liquid discharge port.
Below by several specific embodiments the present invention is done specific description.
Embodiment 1:
At first with purifying upgrading tower (as shown in Figure 1) heat temperature raising to 110 ℃, utilize vacuum control valve that purifying upgrading tower pressure P is controlled to be 1atm (as a comparison), 0.9atm, 0.8atm, 0.7atm, 0.6atm, 0.5atm, 0.4atm, 0.3atm, 0.2atm, 0.1atm, 0.05atm, 0.01atm successively, will consist of H by the liquid flow rate control pump
2SO
4+ 0.1HI+4H
2O (is mol ratio H
2SO
4: HI: H
2O=1: 0.1: 4) sulfuric acid phase, import from purifying upgrading tower top opening for feed, control sulfuric acid phase flow rate of liquid is 183g/h, the reversed reaction that flow through the mutually purifying upgrading tower of temperature control and low pressure of sulfuric acid, the sulfuric acid a small amount of hydroiodic acid HI in mutually and part of sulfuric acid generation Benson react: H
2SO
4+ 2HI=SO
2+ I
2+ 2H
2The SO that O, purification reaction obtain
2, I
2And H
2O is extracted out and is delivered to the Benson reactor from purifying upgrading tower upper end venting port by vacuum control valve, thereby reaches the purpose of purification of sulphuric acids phase.The sulfuric acid of purifying flows into the refined solution storage tank from purifying upgrading tower lower end liquid outlet opening.
(change of 110 ℃ of overdraft is to H in HI transformation efficiency, the refined solution for the model analysis result of purification reaction such as Fig. 2
2SO
4Mass percent concentration, SO
2Optionally influence with S) and Fig. 3 (change of 110 ℃ of overdraft is to product S O
2And I
2The influence of partition ratio in each phase) shown in.As can be seen from Figure 2, under 110 ℃ of normal pressures (1atm), the transformation efficiency of HI is 99.1%, H in the refined solution
2SO
4Mass percent concentration is 55.9%, SO
2Be respectively 22% and 78% with the S selectivity, this just explanation purge process takes place under this condition mainly is the side reaction that generates sulphur, and purifying under low pressure, the transformation efficiency of HI, H
2SO
4Mass percent concentration and SO
2Selectivity all can improve, when pressure is 0.8atm, SO
2Selectivity reach 100%, this shows that purification reaction has only Benson reaction reversed reaction, when pressure was 0.4atm, the transformation efficiency of HI reached 100%, when pressure is 0.05atm, the not only transformation efficiency of HI and SO
2Selectivity all reach 100%, and H in the refined solution
2SO
4Mass percent concentration reaches 77.5%, and this is explanation just, adopts the low pressure purifying can impel the conversion of HI, suppresses the generation of side reaction, and can realize concentrating the sulfuric acid phase.The change of 110 ℃ of overdraft that provide from Fig. 3 is to product S O
2And I
2The influence of partition ratio in each phase as can be seen, normal pressure purified product iodine mainly exists with solid-state, this also is unfavorable for that iodine returns the Benson reaction, and product S O
2Mainly be present in the refined solution, also be unfavorable for SO
2Return the Benson reaction.And along with the reduction of pressure, iodine and SO
2Partition ratio in gas phase increases gradually, and as when pressure is reduced to 0.3atm by 1atm, the partition ratio of iodine in gas phase is upgraded to 99.1% by 0, SO
2Partition ratio in gas phase is upgraded to 99.8% by 0.As seen the low pressure purifying can impel product iodine and SO
2Distribution in gas phase, thus help promoting iodine and SO
2Recycling.
Embodiment 2:
At first with purifying upgrading tower (as shown in Figure 1) heat temperature raising to 60 ℃, utilize vacuum control valve that purifying upgrading tower pressure P is controlled to be 0.1atm, 0.09atm, 0.08atm, 0.07atm, 0.06atm, 0.05atm, 0.04atm, 0.03atm, 0.02atm, 0.01atm successively, will consist of H by the liquid flow rate control pump
2SO
4+ 0.1HI+4H
2O (is mol ratio H
2SO
4: HI: H
2O=1: 0.1: 4) sulfuric acid phase, import from purifying upgrading tower top opening for feed, control sulfuric acid phase flow rate of liquid is 183g/h, the reversed reaction that flow through the mutually purifying upgrading tower of temperature control and low pressure of sulfuric acid, the sulfuric acid a small amount of hydroiodic acid HI in mutually and part of sulfuric acid generation Benson react: H
2SO
4+ 2HI=SO
2+ I
2+ 2H
2The SO that O, purification reaction obtain
2, I
2And H
2O is extracted out and is delivered to the Benson reactor from purifying upgrading tower upper end venting port by vacuum control valve, thereby reaches the purpose of purification of sulphuric acids phase.The sulfuric acid of purifying flows into the refined solution storage tank from purifying upgrading tower lower end liquid outlet opening.
(change of 60 ℃ of overdraft is to H in HI transformation efficiency, the refined solution for the model analysis result of purification reaction such as Fig. 4
2SO
4Mass percent concentration, SO
2Optionally influence with S) and Fig. 5 (change of 60 ℃ of overdraft is to product S O
2And I
2The influence of partition ratio in each phase) shown in.As can be seen from Figure 4, when pressure is reduced to 0.06atm by 0.1atm, SO
2Selectivity be upgraded to 100% by 1.35%, the selectivity of sulphur reduces to 0 by 98.65%, this shows that leading reaction becomes Benson reaction reversed reaction by the formation reaction of sulphur.When pressure when 0.06 reduces to 0.01, the not only transformation efficiency of HI and SO
2Selectivity all keep 100%, and H in the refined solution
2SO
4Mass percent concentration is upgraded to 72.6% from 58.4%.The change of 60 ℃ of overdraft that provide from Fig. 5 is to product S O
2And I
2The influence of partition ratio in each phase as can be seen, when pressure was 0.1atm-0.06atm, product iodine mainly existed with solid-state, product S O
2Mainly be present in the refined solution, this is unfavorable for iodine and SO
2Return the Benson reaction.And along with the reduction of pressure, iodine and SO
2Partition ratio in gas phase increases, and when pressure was reduced to 0.01atm by 0.1atm, the partition ratio of iodine in gas phase was upgraded to 99.98% by 0, SO
2Partition ratio in gas phase is upgraded to 99.99% by 0.
Embodiment 3:
At first with purifying upgrading tower (as shown in Figure 1) heat temperature raising respectively to 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 160 ℃, 180 ℃, 200 ℃, utilize vacuum control valve that purifying upgrading tower pressure P is controlled to be 0.06atm, will consist of H by the liquid flow rate control pump
2SO
4+ 0.1HI+4H
2O (is mol ratio H
2SO
4: HI: H
2O=1: 0.1: 4) sulfuric acid phase, import from purifying upgrading tower top opening for feed, control sulfuric acid phase flow rate of liquid is 183g/h, the reversed reaction that flow through the mutually purifying upgrading tower of temperature control and low pressure of sulfuric acid, the sulfuric acid a small amount of hydroiodic acid HI in mutually and part of sulfuric acid generation Benson react: H
2SO
4+ 2HI=SO
2+ I
2+ 2H
2The SO that O, purification reaction obtain
2, I
2And H
2O is extracted out and is delivered to the Benson reactor from purifying upgrading tower upper end venting port by vacuum control valve, thereby reaches the purpose of purification of sulphuric acids phase.The sulfuric acid of purifying flows into the refined solution storage tank from purifying upgrading tower lower end liquid outlet opening.
(0.06atm changes temperature down to H in HI transformation efficiency, the refined solution for the model analysis result of purification reaction such as Fig. 6
2SO
4Mass percent concentration, SO
2Optionally influence with S).As can be seen from Figure 6, be to carry out sulfuric acid phase purifying under the 0.06atm at pressure, in 60-200 ℃ of temperature range, HI transformation efficiency and SO
2Selectivity all near 100%, and with the rising of temperature, H in the refined solution
2SO
4Mass percent concentration increases.When temperature when 60 temperature are raised to 200 ℃, H
2SO
4Mass percent concentration is upgraded to 94.8% from 58.4%.And product S O
2And I
2Partition ratio is all up to more than 99.9% in gas phase, and the purifying of effectively having realized the sulfuric acid phase is with concentrated.
Embodiment 4:
At first, utilize vacuum control valve that purifying upgrading tower pressure P is controlled to be 0.01atm, will consist of H by the liquid flow rate control pump with purifying upgrading tower (as shown in Figure 1) heat temperature raising to 50 ℃
2SO
4+ 0.01HI+4H
2O (is mol ratio H
2SO
4: HI: H
2O=1: 0.01: 4) sulfuric acid phase, from purifying upgrading tower top opening for feed input, control sulfuric acid phase flow rate of liquid is 177g/h, flow through the mutually purifying upgrading tower of temperature control and low pressure of sulfuric acid, the a small amount of hydroiodic acid HI of sulfuric acid in mutually and the reversed reaction of part of sulfuric acid generation Benson reaction, the SO that purification reaction obtains
2, I
2And H
2O is extracted out and is delivered to the Benson reactor from purifying upgrading tower upper end venting port by vacuum control valve, thereby reaches the purpose of purification of sulphuric acids phase.The sulfuric acid of purifying flows into the refined solution storage tank from purifying upgrading tower lower end liquid outlet opening.The model analysis result of purification reaction shows, not only the transformation efficiency SO of HI
2And SO
2Selectivity be 100%, and H in the refined solution
2SO
4Mass percent concentration reaches 68.5%, product S O
2And I
2Partition ratio is all up to more than 99.9% in gas phase, and the purifying of effectively having realized the sulfuric acid phase is with concentrated.
Embodiment 5:
At first, utilize vacuum control valve that purifying upgrading tower pressure P is controlled to be 0.04atm, will consist of H by the liquid flow rate control pump with purifying upgrading tower (as shown in Figure 1) heat temperature raising to 140 ℃
2SO
4+ 0.1HI+0.02I
2+ 4H
2O (is mol ratio H
2SO
4: HI: I
2: H
2O=1: 0.1: 0.02: 4) sulfuric acid phase, import from purifying upgrading tower top opening for feed, control sulfuric acid phase flow rate of liquid is 940g/h, flow through the mutually purifying upgrading tower of temperature control and low pressure of sulfuric acid, the a small amount of hydroiodic acid HI of sulfuric acid in mutually and the reversed reaction of part of sulfuric acid generation Benson reaction, the SO that purification reaction obtains
2, I
2And H
2O is extracted out and is delivered to the Benson reactor from purifying upgrading tower upper end venting port by vacuum control valve, thereby reaches the purpose of purification of sulphuric acids phase.The sulfuric acid of purifying flows into the refined solution storage tank from purifying upgrading tower lower end liquid outlet opening.The model analysis result of purification reaction shows, not only the transformation efficiency SO of HI
2And SO
2Selectivity be 100%, and H in the refined solution
2SO
4Mass percent concentration reaches 86.2%, product S O
2And I
2Partition ratio is all up to more than 99.9% in gas phase, and the purifying of effectively having realized the sulfuric acid phase is with concentrated.
Embodiment 6:
At first, utilize vacuum control valve that purifying upgrading tower pressure P is controlled to be 0.4atm, will consist of H by the liquid flow rate control pump with purifying upgrading tower (as shown in Figure 1) heat temperature raising to 200 ℃
2SO
4+ 0.15HI+0.03I
2+ 5H
2O (is mol ratio H
2SO
4: HI: I
2: H
2O=1: 0.15: 0.03: 5) sulfuric acid phase, import from purifying upgrading tower top opening for feed, control sulfuric acid phase flow rate of liquid is 215g/h, flow through the mutually purifying upgrading tower of temperature control and low pressure of sulfuric acid, the a small amount of hydroiodic acid HI of sulfuric acid in mutually and the reversed reaction of part of sulfuric acid generation Benson reaction, the SO that purification reaction obtains
2, I
2And H
2O is extracted out and is delivered to the Benson reactor from purifying upgrading tower upper end venting port by vacuum control valve, thereby reaches the purpose of purification of sulphuric acids phase.The sulfuric acid of purifying flows into the refined solution storage tank from purifying upgrading tower lower end liquid outlet opening.The model analysis result of purification reaction shows, not only the transformation efficiency SO of HI
2And SO
2Selectivity be 100%, and H in the refined solution
2SO
4Mass percent concentration reaches 85.7%, product S O
2And I
2Partition ratio is respectively 99.99% and 99.73% in gas phase, and the purifying of effectively having realized the sulfuric acid phase is with concentrated.
In order to estimate the two-phase purification effect, table 1 has provided function definition and the calculation formula thereof of estimating sulfuric acid phase purification effect.
Table 1-estimates the function definition and the calculation formula thereof of sulfuric acid phase purification effect
| Function | Definition | Calculation formula [1] | Explanation |
| ??C HI | The transformation efficiency of HI | ??100％-OF HI/IF HIx100％ | |
| ??S I2 | The selectivity of iodine | ??2OF I2/(IF HI-OF HI)??x100％ | |
| ??S k | The selectivity of component k | ??OF k/(IF SA-OF SA)x100％ | ??k＝SO 2，or?S |
| ??D xi | Component i is in the partition ratio of X phase | ??OF xi/OF ix100％ | X=S (Gu), V (gas), or A (liquid) |
Remarks: [1] IF
iBe the charging flow velocity of component i, the mol/h of unit.
OF
iBe the total discharge rate of component i behind the purification reaction, the mol/h of unit.
OF
XiFor component i behind the purification reaction at the discharge rate of X in mutually, X refer to S (Gu), V (gas), or A (liquid) mol/h of unit.
Need to prove, the given analytical results of Fig. 2 to Fig. 6 adopts analog calculation software ESP (Environmental Simulation Program, version 8.1, OLI Systems, Inc.) the thermodynamics analog calculation analytical results that embodiment is carried out, model analysis is based upon the correlated response balance and balances each other on the basis, does not consider the kinetics of reacting.
Above-mentioned studies show that adopts low pressure purifying process of the present invention and low pressure purification devices to come sulfuric acid in the iodine sulphur cycle is carried out purifying mutually, compares with the purifying process of nitrogen purging, need not use nitrogen.Compare with the normal pressure purifying, the low pressure purifying can improve the impurity acid transformation efficiency, improves SO
2Selectivity, impel the reversed reaction of Benson reaction to become the leading reaction of purifying, the low pressure purifying also can impel SO
2And I
2Distribution in gas phase helps I
2And SO
2Recycling.And the purifying for the sulfuric acid phase can a step realize that the two-phase cleansing temp is lower, can improve purification efficiency with concentrated, reduces the purifying cost.As seen this employing invention can effectively remove sulfuric acid mutually in a spot of hydroiodic acid HI, shown good prospects for application.
Claims (2)
1. the processing method of sulfuric acid phase in the sulphur cycle of purifying iodine under the low pressure is characterized in that this method comprises the steps:
1) is controlled to be 0.01atm≤P＜1atm at first with purifying upgrading tower heat temperature raising to 50～200 ℃, and with purifying upgrading tower pressure P; By the liquid flow rate control pump sulfuric acid of known component is imported from purifying upgrading tower top opening for feed then;
2) in the purifying upgrading tower, the hydroiodic acid HI of sulfuric acid in mutually and the reversed reaction of part of sulfuric acid generation Benson reaction: H
2SO
4+ 2HI=SO
2+ I
2+ 2H
2The SO that O, purification reaction obtain
2, I
2And H
2O extracts and is delivered to the Benson reactor out from purifying upgrading tower upper end venting port;
3) sulfuric acid that is purified flows out from the liquid outlet opening of purifying upgrading tower lower end.
2. the device of sulfuric acid phase in the sulphur cycle of purifying iodine under the low pressure that realizes technology according to claim 1, it is characterized in that: the refined solution storage tank (10) that described device comprises stock liquid storage tank (1), purifying upgrading tower (3), vacuum control valve (5), process furnace (7), temperature controller (8) and is arranged on purifying upgrading tower bottom, described stock liquid storage tank is connected with purifying upgrading tower top opening for feed by the pipeline that liquid flow rate adjusting pump (2) is housed; Described vacuum control valve is connected with the venting port at purifying upgrading tower top by venting port stopping valve (4); Described refined solution storage tank is connected by the liquid outlet opening of leakage fluid dram stopping valve (9) with purifying upgrading tower bottom.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553407A (en) * | 2012-01-15 | 2012-07-11 | 浙江大学 | Thermochemical cycle reaction system for decomposing CO2And H2O method and device |
| CN102583239A (en) * | 2012-01-15 | 2012-07-18 | 浙江大学 | Method and device for preparing CO and H2 by thermochemical cycle decomposition of CO2 and H2O |
| CN105775779A (en) * | 2014-12-26 | 2016-07-20 | 中核建中核燃料元件有限公司 | Device and method for treating high-fluorine materials |
| CN110510576A (en) * | 2019-08-20 | 2019-11-29 | 中核能源科技有限公司 | A kind of high temperature gas cooled reactor coupling iodine selenium thermochemical cycles electrolytic hydrogen production method |
| CN113402362A (en) * | 2021-06-25 | 2021-09-17 | 国能经济技术研究院有限责任公司 | CO of chemical hydrogen production2Zero-emission coal-to-methanol system and method and application |
| CN116161623A (en) * | 2023-04-21 | 2023-05-26 | 浙江百能科技有限公司 | Method and device for purifying and concentrating HIx phase of thermochemical sulfur-iodine cyclic hydrogen production |
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| CN1785796A (en) * | 2005-10-14 | 2006-06-14 | 浙江大学 | Technical method of sulfur iodine open circuit circulation hydrogen manufacture and its equipment |
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| CN1785796A (en) * | 2005-10-14 | 2006-06-14 | 浙江大学 | Technical method of sulfur iodine open circuit circulation hydrogen manufacture and its equipment |
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| 《Chinese Journal of Chemical Engineering》 20090228 Bai Ying et al Purification of Sulfuric and Hydriodic Acids Phases in the Iodine-sulfur Process 161-166页2.2和3.1内容，图3,图4 1、2 第17卷, 第1期 2 * |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102553407A (en) * | 2012-01-15 | 2012-07-11 | 浙江大学 | Thermochemical cycle reaction system for decomposing CO2And H2O method and device |
| CN102583239A (en) * | 2012-01-15 | 2012-07-18 | 浙江大学 | Method and device for preparing CO and H2 by thermochemical cycle decomposition of CO2 and H2O |
| CN102583239B (en) * | 2012-01-15 | 2013-10-30 | 浙江大学 | Method and device for preparing CO and H2 by thermochemical cycle decomposition of CO2 and H2O |
| CN105775779A (en) * | 2014-12-26 | 2016-07-20 | 中核建中核燃料元件有限公司 | Device and method for treating high-fluorine materials |
| CN105775779B (en) * | 2014-12-26 | 2018-05-18 | 中核建中核燃料元件有限公司 | A kind of apparatus and method for handling high fluorine material |
| CN110510576A (en) * | 2019-08-20 | 2019-11-29 | 中核能源科技有限公司 | A kind of high temperature gas cooled reactor coupling iodine selenium thermochemical cycles electrolytic hydrogen production method |
| CN110510576B (en) * | 2019-08-20 | 2020-12-11 | 中核能源科技有限公司 | High-temperature gas cooled reactor coupled iodine selenium thermochemical cycle electrolysis hydrogen production method |
| CN113402362A (en) * | 2021-06-25 | 2021-09-17 | 国能经济技术研究院有限责任公司 | CO of chemical hydrogen production2Zero-emission coal-to-methanol system and method and application |
| CN113402362B (en) * | 2021-06-25 | 2022-02-11 | 国能经济技术研究院有限责任公司 | CO of chemical hydrogen production2Zero-emission coal-to-methanol system and method and application |
| CN116161623A (en) * | 2023-04-21 | 2023-05-26 | 浙江百能科技有限公司 | Method and device for purifying and concentrating HIx phase of thermochemical sulfur-iodine cyclic hydrogen production |
| CN116161623B (en) * | 2023-04-21 | 2023-07-07 | 浙江百能科技有限公司 | Method and device for purifying and concentrating HIx phase of thermochemical sulfur-iodine cyclic hydrogen production |
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