CN101732945A - Method for recovering hydrogen from tail gas containing chlorsilane - Google Patents
Method for recovering hydrogen from tail gas containing chlorsilane Download PDFInfo
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Abstract
The invention discloses a method for recovering hydrogen from tail gas containing chlorsilane. The method comprises the following steps of: by a pressure-swing absorption method, performing pressure-swing absorption process for absorption and desorption on raw gas respectively through each absorption tower in a pressure-swing absorption system consisting of at least three absorption towers to obtain purified hydrogen, and performing circulatory operation in each absorption tower respectively according to the conventional pressure-swing absorption process. Absorption agents filled in the absorption towers comprise alumina, silica gel, active carbon and molecular sieves. The method can effectively separate and recover pure hydrogen from gases containing hydrogen, chlorine hydride, chlorsilane and the like, the recovery yield of hydrogen is high, the content of impurities of chlorine hydride, chlorsilane and the like remained in the product is low, the hydrogen purity is high, and simultaneously the components of chlorine hydride, chlorsilane and the like in the product can be separated and recovered. The equipment cost is low, the process is simple, and the energy consumption is low.
Description
Technical field
The invention belongs to gas separation technique field, particularly a kind of from the tail gas of chlorine-containing silanes such as polysilicon or trichlorosilane the method for recover hydrogen.
Background technology
Greatly develop under the background that new forms of energy replace traditional energy in society now, polysilicon, trichlorosilane industry be gradually by popular and society's understanding, and become the focus of attention rapidly.But in its production process, will produce the process tail gas of components such as main hydrogen, hydrogen chloride, trichlorosilane.Its tail gas component is shown in following table 1:
Table 1 polysilicon, trichlorosilane tail gas component
| Component | ??H 2 | ??HCl | ??SiHCl 3、SiCl 4、SiH 2Cl 2 | ??N 2 |
| Form (V%) | ??79～96 | ??3～17.84 | ??1～2.97 | ??0～0.19 |
Owing to wherein contain the chlorosilane composition, and chlorosilane belongs to heavy contaminant, can not directly discharge or hydrogen be recycled without handling.
Remove compositions such as hydrogen chloride in the tail gas, chlorosilane and reach the purpose of recover hydrogen, the method that past adopts water to absorb usually, allow tail gas pass through alkaline water, impurity component such as hydrogen chloride, chlorosilane and buck react and are removed, hydrogen is recovered after by buck, but the method is brought a large amount of sewage and can't be handled.Hydrogen in many now employing alternating temperature absorption+rectifying freezings separation polysilicons or the trichlorosilane and hydrogen chloride, chlorosilane composition, but the method is except needs alternating temperature adsorption tower, also increased equipment such as absorption tower, rectifying column and refrigeration system, the dispensable mould cost of investment is higher; And because equipment is more, the also corresponding increase of operating cost is increased at the complicated control point of process route; Because the existence of alternating temperature, rectifying and operating unit such as freezing, increased the energy consumption of process in addition.Thereby this method is less at present is used.
Transformation absorption (Pressure Swing Adsorption, PSA) be a kind of physical adsorption process that adsorbs by the molecular force between adsorbent and the adsorbate (comprising Van der Waals force and electromagnetic force), be characterized in adsorption process, there is not chemical reaction, adsorption process is carried out to such an extent that be exceedingly fast, dynamic equilibrium between each the phase material that participates in adsorbing can be finished instantaneous, and absorption is reversible.Therefore, all be included in absorption under the condition of high voltage and the steps such as desorb under the low pressure condition in the basic process of transformation absorption.The application of transformation absorption at present is very extensive, has successfully applied to H
2, CH
4, O
2, N
2, CO
2Separate with gases such as other hydro carbons, recovery and field of refinement.This technology has investment and operating cost is low, non-environmental-pollution and equipment corrosion, technology is simple, the adsorbent life-span is long, operating flexibility is big, start stop operation is convenient, automaticity is high, suitable source of the gas is wide, product purity is high and many distinguishing features such as energy-saving and cost-reducing.
The physical characteristic of the adsorbent that is utilized by recover hydrogen in polysilicon or the trichlorosilane tail gas is that adsorbent is different with the adsorption capacity of impurity composition to hydrogen, and the adsorption capacity of impurity composition on adsorbent rises with dividing potential drop and increases, and rising with adsorption temp descends.The former can make the impurity preferential adsorption in the unstripped gas of hydrogen, and hydrogen is purified, and the latter then can make adsorbent adsorb under low temperature or high pressure, and desorb is regenerated under high temperature or low pressure.Thereby realize the absorption and the regeneration of adsorbent, reach continuous purification and separate the purpose of purifying.
For example: Chinese patent ZL 97105007.4 discloses a kind of employing raw hydrogen (＞99.00%) is produced high-purity hydrogen (can＞99.999%) through pressure swing adsorption method method; Application number be 88105937.4 Chinese patent application disclose a kind of from synthesizing methanol speeds to exit the pressure swing adsorption method of recover hydrogen; Chinese patent ZL 200510060453.4 disclose a kind of from careless glycosides phosphonic acids process gas the recovery method of purification of hydrogen; Chinese patent ZL 97107640.5 discloses a kind of improvement pressure swing adsorption method that extracts hydrogen from synthetic ammonia relief gas, methyl alcohol such as speed to exit at rich hydrogen waste gas; Application number is that 97107735.5 Chinese patent application discloses a kind of multi-bed vacuum pressure swing adsorption process that extracts hydrogen from hydrogeneous gaseous mixture.
Owing to contain impurity components such as hydrogen chloride and chlorosilane in polysilicon or the trichlorosilane tail gas, easy absorption under normal temperature condition is difficult to resolve suction and adsorbent is to impurity components such as hydrogen chloride and chlorosilanes, so the retracting device that adopts the normal temperature condition operation after adsorbent fully absorbs, thoroughly desorb.Simultaneously, because hydrogen chloride is sour gas, easily adsorbent and equipment are caused corrosion; Easy and the water reaction generation silica solid of chlorosilane, thus the hole of obstruction adsorbent causes performance of the adsorbent to descend even inefficacy.Therefore, traditional adsorbent equipment and aspects such as adsorption process arrangement, the design of adsorbent loadings thereof all can not satisfy separating of hydrogen chloride and impurity components such as chlorosilane in polysilicon or the trichlorosilane tail gas.
Summary of the invention
Main purpose of the present invention is at above-mentioned the deficiencies in the prior art, especially the requirement that can't satisfy impurity such as removing hydrogen chloride and chlorosilane at common pressure swing absorption process causes that the product hydrogen purity is lower, impurity content is higher, hydrogen recovery rate is low, and adopt that alternating temperature absorption+rectifying freezing separates that cost is higher, complex process, the also high weak point of energy consumption, a kind of method with transformation suction type separating and reclaiming hydrogen from the tail gas of chlorine-containing silanes such as polysilicon or trichlorosilane newly is provided.Purified hydrogen can effectively be separated, be reclaimed to this method from the gas that contains compositions such as hydrogen, hydrogen chloride and chlorosilane, the rate of recovery height of hydrogen, impurity content such as residual hydrogen chloride and chlorosilane is low in the product that obtains, the hydrogen purity height, and equipment cost is more cheap, technology is more simple, also energy efficient more simultaneously.
In order to realize the foregoing invention purpose, the technical solution used in the present invention is as follows:
The method of recover hydrogen from tail gas containing chlorsilane, adopt pressure swing adsorption method, make the unstripped gas (tail gas that promptly refers to components such as hydrogen, chlorosilane, tail gas as components such as hydrogen such as polysilicon or trichlorosilane, chlorosilane and hydrogen chloride) in each adsorption tower of the pressure swing adsorption system that comprises at least three (can be preferably 3～20) adsorption towers successively through the absorption and the pressure-swing absorption process of desorb, obtain the hydrogen of purifying; In each adsorption tower respectively the pressure-swing absorption process according to routine carry out cycling.
In order to satisfy the requirement that removes impurity such as hydrogen chloride and chlorosilane, improve the purity of hydrogen in hydrogen recovery rate and the product gas, the content of impurity in the reduction product gas, in the above-mentioned pressure-swing absorption process, it is crucial that the kind of adsorbent selects to reach suitably collocation etc.
By in a large number, repeatedly experimental study and comparative analysis, the inventor has determined finally preferably to be applicable to that the adsorbent of recover hydrogen technology from tail gas containing chlorsilane comprises at least: active carbon, silica gel, molecular sieve.On this basis, according to actual needs, can also further select adsorbents such as aluminium oxide for use.Aluminium oxide whether select for use and loadings is decided by the content of hydrogen chloride in the processed gaseous mixture and chlorosilane impurity and/or tolerance load, impurity content and/or large-minded, then the ratio of loading can suitably increase.
Above-mentioned each adsorbent can fill in the different parts of same adsorption tower in proper order according to absorption, also can fill in proper order in the different adsorption towers according to absorption.
The loadings of adsorbents such as active carbon, silica gel, molecular sieve, aluminium oxide can suitably increase and decrease according to the amount of unstripped gas.Said adsorbent of molecular sieve can be preferably the 5A molecular sieve especially.
In each adsorption tower, the pressure-swing absorption process of routine generally includes: absorption (A), all pressure drops (EnD), contrary (D), flushing (P) and/or find time (V), equal voltage rise (EnR) and the steps such as (FR) of finally boosting of putting; When " wash and/or find time " comprises " flushing " operation, after equal pressure drops, before contrary the putting, also can carry out along putting (PP) operation.
The increase and decrease selection of each step and the arrangement of sequence of steps can be carried out choose reasonable and/or adjustment according to parameters such as concrete PROCESS FOR TREATMENT required pressure, purity.
In the pressure-swing absorption process, " absorption " with unstripped gas or from the corresponding impurity absorption in the gas of last adsorption tower in adsorbent, make impurity therefrom obtain separating; " all pressure drops, (along put) contraryly put, wash or find time " and continuous operation, the impurity that is adsorbed in the adsorbent is separated by desorb, make adsorbent obtain regeneration, be the regenerative process of adsorbent.
Above-mentioned pressure-swing absorption process generally can be carried out in the pressure swing adsorption system that comprises 3～20 adsorption towers, wherein in each adsorption tower respectively according to routine pressure-swing absorption process carry out cycling, just each adsorption tower staggers on sequential mutually, carries out continuously to guarantee removal process such as absorption, desorb.Be to guarantee the continuity of technology, also can increase in actual use 2～6 not the slack tank of filled with adsorbent use as equalizer tank; In order to guarantee that product gas more stably exports, in design, also can increase by 1～3 product gas surge tank.Wherein, to the selection of the adsorptive pressure of adsorption tower in the PSA processing procedure, depend primarily on the trichlorosilane of processed hydrogen-containing gas or the emptying exhaust gas pressure of polysilicon.In the separation recycling process of the above-mentioned PSA of the present invention system, be feasible adsorptive pressure as long as can overcome the pressure of SR.Test shows that generally adsorption process all can be finished smoothly under gauge pressure 0.04～3.0MPa condition.
In reclaiming the desorption process of technology, can require to select flexibly according to difference to product hydrogen and (or) adjust and find time and/or rinsing step.According to actual needs, the concrete selection of said flushing and/or evacuation both can only be adopted rinsing step or evacuation step separately, the operation that also can adopt the mode of appropriate combination to carry out said flushing and find time simultaneously or sequentially.In the concrete compound mode, for example can adopt and carry out flushing operation earlier, and then the combination of employing evacuation step, also can adopt and carry out evacuation step earlier and adopt rinsing step again, can also carry out rinsing step in the overall process of evacuation step or in the part-time simultaneously, or in the overall process of rinsing step or part-time, carry out various ways such as evacuation step simultaneously.For example, not too high when purity requirement to product hydrogen, then can only adopt single rinsing step; When needing the higher hydrogen of production purity, can cooperate the employing evacuation step, even need to adopt simultaneously to find time and rinsing step, just can make the adsorbent reactivation of saturated absorption impurity more thorough, thereby guaranteeing that clean absorption forward position can be adsorbed control impurity and obtain the high-purity hydrogen product.If the rate of recovery of hydrogen is had relatively high expectations (as＞90%), then need adopt evacuation step to the regeneration of adsorbent; If when the rate of recovery is required to hang down, can adopt rinsing step.
Compared with prior art, the invention has the beneficial effects as follows:
Adopt the inventive method, can effectively handle tail gas such as the polysilicon that contains hydrogen, hydrogen chloride and chlorosilane, trichlorosilane.Hydrogen chloride in the gaseous mixture (tail gas) and chlorosilane impurity, be attracted to during by adsorption tower adsorbent bed in, obtain highly purified purified hydrogen by the pressure swing adsorption system port of export, make hydrogen obtain satisfied recycling, simultaneously also can be further components such as wherein hydrogen chloride and chlorosilane be carried out desorb, thereby make it effectively to be separated recovery.Show that by a large amount of tests the purity of resulting high concentration product hydrogen can reach 99.99999% (mol) after the present invention sends out the method processing, wherein the concentration of impurity such as hydrogen chloride and chlorosilane can be lower than 1 * 10 respectively
-6, can be reached for 85%～95% usually to the rate of recovery of hydrogen component.Recover hydrogen can be delivered to the gas operation as polysilicon or trichlorosilane raw materials for production gas as product gas.Absorption finish the back by contraryly put and wash/or the stripping gas of finding time to obtain can be through condenser condenses separating hydrogen chloride and chlorosilane, the unstripped gas that hydrogen chloride can be used as trichlorosilane reuses, chlorosilane is then treated rectifying as crude product.In reclaiming the desorption process of technology, can select flexibly and (or) adjust and find time and/or rinsing step, satisfy the practical condition needs on to greatest extent, satisfy different hydrogen purity requirements; Reach the rate of recovery of different hydrogen purity; Adapt to foreign gas constituent content condition in different polysilicons, the trichlorosilane tail gas.With other technology relatively, this technology requires to reduce to the pressure of raw material tail gas, can reach better level to the rate of recovery of hydrogen, it is wider to be suitable for density of hydrogen and pressure, economic benefit and environmental benefit are also even more ideal.
Description of drawings
Fig. 1 is each section of pressure swing adsorption system schematic flow sheet of embodiment 1;
Fig. 2 is each section of pressure swing adsorption system schematic flow sheet of embodiment 2;
Fig. 3 is each section of pressure swing adsorption system schematic flow sheet of embodiment 3.
The specific embodiment
Below in conjunction with the specific embodiment foregoing invention content of the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Not breaking away under the above-mentioned technological thought situation of the present invention, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
Embodiment 1
Present embodiment is 9 tower pressure swing adsorption methods of recover hydrogen from trichlorosilane tail gas (raw material tail gas), and the raw material exhaust flow is about 200Nm
3/ Hr, adsorptive pressure is about 0.6MpaG; The composed as follows of raw material tail gas stated shown in the table 2:
The composition of table 2 embodiment 1 raw material tail gas
| Component | ??H 2 | ??HCl | ??SiHCl 3、SiCl 4、SiH 2Cl 2 | ??N 2 |
| Form (V%) | ??79.00 | ??17.84 | ??2.97 | ??0.19 |
Pressure swing adsorption system divides 3 sections (series connection) in the present embodiment, by totally 9 adsorption towers, 3 vavuum pumps and corresponding sequencing valve, pipeline etc. are formed by connecting.The technological process of each section as shown in Figure 1,, wherein T201A/B/C is an adsorption tower, V201 is a surge tank, P201 is a vavuum pump, 1A/B/C, 2A/B/C, 3A/B/C/D, 4A/B/C/D, 5A/B/C/E, 6A/B/C etc. are sequencing valve.Every section comprises 3 adsorption towers respectively; Wherein, be loaded on each adsorption tower of first section and second section after aluminium oxide, silica gel, three kinds of adsorbents of active carbon mixed by 1: 1: 1 (mass ratio), molecular sieve is loaded on each adsorption tower of the 3rd section.Each section adopts identical sequential flow process (shown in following table 3), and adsorptive pressure is about: 0.6MPaG; Each adsorption tower that is in adsorbed state simultaneously is 3,1 every section.
Cycling process in each adsorption tower is identical, but evenly staggers on the time; Shown in following table 3, the cycling process of adsorption tower is in each section: A → E1D → D → V → E1R → FR.
The circulation time-scale of table 3 embodiment 1 each adsorption tower
| ??1 | ??A | ??A | ??A | ??E1D | ??D | ??V | ??E1R | ??FR | ??FR |
| ??2 | ??E1R | ??FR | ??FR | ??A | ??A | ??A | ??E1D | ??D | ??V |
| ??3 | ??E1D | ??D | ??V | ??E1R | ??FR | ??FR | ??A | ??A | ??A |
When system moved, each sequencing valve was by the computer program gauge tap of setting.The trichlorosilane tail gas of about 0.6MPaG (raw material tail gas) enters pressure swing adsorption system through the unstripped gas pipeline.Raw material tail gas enters adsorption tower after being heated to 40 ℃ through heater earlier, and in adsorption tower, most of hydrogen chloride wherein, chlorosilane rest on one section.With a tower is example, adsorption tower successively through absorption (A), a step-down (E1D), reversely put pressures (D), vacuumize (V), once boost (E1R) reach the step (FR) of finally boosting.Finish a work period of a tower like this, many adsorption tower absorption in turn guarantee to adsorb stable carrying out.Part hydrogen chloride, chlorosilane rest on two sections, and other small amount of impurities such as nitrogen rests on three sections.Two sections operating processes with three sections are identical with one section.The impurity of trace is collected by three sections adsorption tower tops with hydrogen and is obtained, and exports as product gas.Be adsorbed in hydrogen chloride in the adsorption tower and chlorosilane composition through step-down, contrary put and step such as find time after collect by tower bottom and to obtain.
Present embodiment is a hydrogen purity 99.0% to the requirement of hydrogen purity, and hydrogen recovery rate is required 〉=95%.Because the rate of recovery to product hydrogen requires height, in the process of adsorption tower regeneration, adopted the mode that vacuumizes.
After above-mentioned processing, in the product gas that obtains, hydrogen content 〉=99.0%.
Embodiment 2
Present embodiment is 12 tower pressure swing adsorption methods of recover hydrogen from trichlorosilane tail gas (raw material tail gas), and the raw material exhaust flow is about 600Nm
3/ Hr, adsorptive pressure is about 0.5MpaG; The composed as follows of raw material tail gas stated shown in the table 4:
The composition of table 4 embodiment 2 raw material tail gas
| Component | ??H 2 | ??HCl | ??SiHCl 3、SiCl 4、SiH 2Cl 2 | ??N 2 |
| Form (V%) | ??79.00 | ??17.84 | ??2.97 | ??0.19 |
Pressure swing adsorption system divides 3 sections (series connection) in the present embodiment, by totally 12 adsorption towers, 3 vavuum pumps and corresponding sequencing valve, pipeline etc. are formed by connecting.
The technological process of each section as shown in Figure 2, wherein T201A/B/C/D is an adsorption tower, V201 is a surge tank, P201A is a vavuum pump, 1A/B/C/D, 2A/B/C/D, 3A/B/C/D/F, 4A/B/C/D/F, 5A/B/C/D, 6A/B/C/D etc. are sequencing valve.Every section comprises 4 adsorption towers respectively; Wherein, be loaded on each adsorption tower of first section and second section after aluminium oxide, silica gel, three kinds of adsorbents of active carbon mixed by 1: 1: 1 (mass ratio), molecular sieve is loaded on each adsorption tower of the 3rd section.
Cycling process in each adsorption tower is identical, but evenly staggers on the time; Shown in following table 5, the cycling process of adsorption tower is in each section: A → E1D → E2D → D → V → E2R → E1R → FR.
The circulation time-scale of table 5 embodiment 2 each adsorption tower
| ??1 | ??A | ??A | ??A | ??A | ??E1D | ??～ | ??E2D | ??D | ??V | ??V | ??E2R | ??～ | ??E1R | ??FR | ??FR | ??FR |
| ??2 | ??E1R | ??FR | ??FR | ??FR | ??A | ??A | ??A | ??A | ??E1D | ??～ | ??E2D | ??D | ??V | ??V | ??E2R | ??～?? |
| ??3 | ??V | ??V | ??E2R | ??～ | ??1R | ??FR | ??FR | ??FR | ??A | ??A | ??A | ??A | ??E1D | ??～ | ??E2D | ??D |
| ??4 | ??E1D | ??～ | ??E2D | ??D | ??V | ??V | ??E2R | ??～ | ??E1R | ??FR | ??FR | ??FR | ??A | ??A | ??A | ??A |
When system moved, each sequencing valve was by the computer program gauge tap of setting.The trichlorosilane tail gas of about 0.5MPaG (raw material tail gas) enters pressure swing adsorption system through the unstripped gas pipeline.Raw material tail gas enters adsorption tower after being heated to 40 ℃ through heater earlier, and in adsorption tower, most of hydrogen chloride wherein, chlorosilane rest on one section.With a tower is example, adsorption tower successively through absorption (A), a step-down (E1D), secondary step-down (E2D), reversely put pressures (D), vacuumize (V), secondary booster (E2R), once boost (E1R) reach the step (FR) of finally boosting.Finish a work period of a tower like this, many adsorption tower absorption in turn guarantee to adsorb stable carrying out.Part hydrogen chloride, chlorosilane rest on two sections, and other small amount of impurities such as nitrogen rests on three sections.Two sections operating processes with three sections are identical with one section.The impurity of trace is collected by three sections adsorption tower tops with hydrogen and is obtained, and exports as product gas.Be adsorbed in hydrogen chloride in the adsorption tower and chlorosilane composition through step-down, contrary put and step such as find time after collect by tower bottom and to obtain.
Present embodiment is a hydrogen purity 99.0% to the requirement of hydrogen purity, and hydrogen recovery rate is required 〉=95%.Because the rate of recovery to product hydrogen requires height, in the process of adsorption tower regeneration, adopted the mode that vacuumizes.
After above-mentioned processing, in the product gas that obtains, hydrogen content 〉=99.0%.
Embodiment 3
Present embodiment is 18 tower pressure swing adsorption methods of recover hydrogen from trichlorosilane tail gas (raw material tail gas), and the raw material exhaust flow is about 600Nm
3/ Hr, adsorptive pressure is about 0.7MpaG; The composed as follows of raw material tail gas stated shown in the table 6:
The composition of table 6 embodiment 3 raw material tail gas
| Component | ??H 2 | ??HCl | ??SiHCl 3、SiCl 4、SiH 2Cl 2 | ??N 2 |
| Form (V%) | ??79.00 | ??17.84 | ??2.97 | ??0.19 |
Pressure swing adsorption system divides 3 sections (series connection) in the present embodiment, by totally 18 adsorption towers, 3 vavuum pumps and corresponding sequencing valve, pipeline etc. are formed by connecting.
The technological process of each section as shown in Figure 3, wherein T101A～F is an adsorption tower, V101, V102 are that surge tank, P101A are vavuum pump, 1A～F, 2A～F, 3A～F, 4A～F/H, 5A～F/H, 6A～F/H, 7A～F etc. are sequencing valve.Every section comprises 6 adsorption towers respectively; Wherein, be loaded on each adsorption tower of first section and second section after aluminium oxide, silica gel, three kinds of adsorbents of active carbon mixed by 1: 1: 1 (mass ratio), molecular sieve is loaded on each adsorption tower of the 3rd section.
Cycling process in each adsorption tower is identical, but evenly staggers on the time; Shown in following table 7, the cycling process of adsorption tower is in each section: A → 1D → 2D → 3D → 4D → 5D → D → V → 5R → 4R → 3R → 2R → 1R → FR.
The circulation time-scale of table 7 embodiment 3 each adsorption tower
| ??1 | ??A | ??A | ??A | ??A | ??1??D | ??2??D | ??3??D | ??4??D | ??5??D | ??D | ??V | ??V | ??V | ??V | ??R | ??R | ??5??R | ??4??R | ??3??R | ??2??R | ??1??R | ??F??R | ??F??R | ??F??R |
| ??2 | ??1??R | ??F??R | ??F??R | ??F??R | ??A | ??A | ??A | ??A | ??1??D | ??2??D | ??3??D | ??4??D | ??5??D | ??D | ??V | ??V | ??V | ??V | ??R | ??R | ??5??R | ??4??R | ??3??R | ??2??R |
| ??1 | ??A | ??A | ??A | ??A | ??1??D | ??2??D | ??3??D | ??4??D | ??5??D | ??D | ??V | ??V | ??V | ??V | ??R | ??R | ??5??R | ??4??R | ??3??R | ??2??R | ??1??R | ??F??R | ??F??R | ??F??R |
| ??3 | ??5??R | ??4??R | ??3??R | ??2??R | ??1??R | ??F??R | ??F??R | ??F??R | ??A | ??A | ??A | ??A | ??1??D | ??2??D | ??3??D | ??4??D | ??5??D | ??D | ??V | ??V | ??V | ??V | ??R | ??R |
| ??4 | ??V | ??V | ??R | ??R | ??5??R | ??4??R | ??3??R | ??2??R | ??1??R | ??F??R | ??F??R | ??F??R | ??A | ??A | ??A | ??A | ??1D | ??2??D | ??3??D | ??4??D | ??5??D | ??D | ??V | ??V |
| ??5 | ??5??D | ??D | ??V | ??V | ??V | ??V | ??R | ??R | ??5??R | ??4??R | ??3??R | ??2??R | ??1??R | ??F??R | ??F??R | ??F??R | ??A | ??A | ??A | ??A | ??1??D | ??2??D | ??3??D | ??4??D |
| ??6 | ??1??D | ??2??D | ??3??D | ??4??D | ??5??D | ??D | ??V | ??V | ??V | ??V | ??R | ??R | ??5??R | ??4??R | ??3??R | ??2??R | ??1??R | ??F??R | ??F??R | ??F??R | ??A | ??A | ??A | ??A |
When system moved, each sequencing valve was by the computer program gauge tap of setting.The trichlorosilane tail gas of about 0.7MPaG (raw material tail gas) enters pressure swing adsorption system through the unstripped gas pipeline.Raw material tail gas enters adsorption tower after being heated to 40 ℃ through heater earlier, and in adsorption tower, most of hydrogen chloride wherein, chlorosilane rest on one section.With a tower is example, adsorption tower successively through absorption (A), a step-down (1D), secondary step-down (2D), three step-downs (3D), four step-downs (4D), five step-downs (5D), reversely put pressures (D), vacuumize (V), boost for five times (5R), boost for four times (4R), boost for three times (3R), secondary booster (2R), once boost (1R) reach the step (FR) of finally boosting.Finish a work period of a tower like this, many adsorption tower absorption in turn guarantee to adsorb stable carrying out.Part hydrogen chloride, chlorosilane rest on two sections, and other small amount of impurities such as nitrogen rests on three sections.Two sections operating processes with three sections are identical with one section.The impurity of trace is collected by three sections adsorption tower tops with hydrogen and is obtained, and exports as product gas.Be adsorbed in hydrogen chloride in the adsorption tower and chlorosilane composition through step-down, contrary put and step such as find time after collect by tower bottom and to obtain.
Present embodiment is a hydrogen purity 99.0% to the requirement of hydrogen purity, and hydrogen recovery rate is required 〉=95%.Because the rate of recovery to product hydrogen requires height, in the process of adsorption tower regeneration, adopted the mode that vacuumizes.
After above-mentioned processing, in the product gas that obtains, hydrogen content 〉=99.0%.
Claims (9)
1. the method for recover hydrogen from tail gas containing chlorsilane, adopt pressure swing adsorption method, make unstripped gas in each adsorption tower of the pressure swing adsorption system that comprises three adsorption towers, pass through the pressure-swing absorption process of absorption and desorb at least successively, obtain the hydrogen of purifying, in each adsorption tower respectively the pressure-swing absorption process according to routine carry out cycling; It is characterized in that: the adsorbent that loads in adsorption tower comprises silica gel, active carbon and molecular sieve.
2. method according to claim 1 is characterized in that: described sorbent molecule sieve is the 5A molecular sieve.
3. method according to claim 1 is characterized in that: described adsorbent silica gel, active carbon, molecular sieve, fill in the different parts of same adsorption tower, and perhaps fill in the different adsorption towers.
4. method according to claim 1 is characterized in that: described pressure swing adsorption system comprises 3～20 adsorption towers.
5. according to each described method among the claim 1-4, it is characterized in that: the adsorptive pressure when described each adsorption tower adsorbs is gauge pressure 0.04～3.0MPa.
6. according to each described method among the claim 1-4, it is characterized in that: described pressure-swing absorption process comprises: absorption, all pressure drops, contraryly put, wash and/or find time, all voltage rises, finally boost.
7. according to each described method among the claim 1-4, it is characterized in that: described pressure-swing absorption process comprises: absorption, all pressure drops, along putting, contraryly put, wash, all voltage rises, finally boosting.
8. according to each described method among the claim 1-4, it is characterized in that: described pressure-swing absorption process comprises: absorption, all pressure drops, along putting, contraryly put, wash and find time, all voltage rises, finally boosting.
9. according to each described method among the claim 1-4, it is characterized in that: described unstripped gas is the tail gas of polysilicon or trichlorosilane.
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| CN200910263587A Pending CN101732945A (en) | 2009-12-25 | 2009-12-25 | Method for recovering hydrogen from tail gas containing chlorsilane |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030312A (en) * | 2010-12-23 | 2011-04-27 | 江西嘉柏新材料有限公司 | Method for recovering hydrogen gas from trichlorosilane tail gas |
| CN103170214A (en) * | 2013-04-15 | 2013-06-26 | 四川天一科技股份有限公司 | Method for recovering methane chloride from organic silicon synthetic tail gas |
| CN103588170A (en) * | 2013-11-15 | 2014-02-19 | 新特能源股份有限公司 | Treatment process for purifying recycled hydrogen during production of electronic-grade polycrystalline silicon |
| CN104556042A (en) * | 2014-12-29 | 2015-04-29 | 新疆大全新能源有限公司 | Polycrystalline silicon production method and equipment based on improved Siemens method |
| CN105169889A (en) * | 2015-10-26 | 2015-12-23 | 四川天一科技股份有限公司 | Pressure swing adsorption process for cascade purging |
| CN107344058A (en) * | 2017-09-08 | 2017-11-14 | 成都盛利达科技有限公司 | A kind of hydrogen chloride gas advanced purification process of energy-conservation |
| CN108926960A (en) * | 2018-08-31 | 2018-12-04 | 四川永祥新能源有限公司 | A kind of processing method of cold hydrogenated tail gas |
| CN109529534A (en) * | 2018-12-27 | 2019-03-29 | 四川天科技股份有限公司 | A kind of method and device for purifying organosilicon fractionation tail gas and recycling organic silicon monomer |
| CN109790020A (en) * | 2016-09-26 | 2019-05-21 | 住友精化株式会社 | The refining methd and hydrogen of hydrogen or helium or the refining plant of helium |
| CN110550605A (en) * | 2018-06-04 | 2019-12-10 | 国家能源投资集团有限责任公司 | Device and method for preparing high-purity hydrogen from hydrogen-containing gas |
| CN110639328A (en) * | 2019-09-16 | 2020-01-03 | 新疆大全新能源股份有限公司 | Method for removing trace carbon impurities in tail gas recovery hydrogen treatment process |
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2009
- 2009-12-25 CN CN200910263587A patent/CN101732945A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102030312A (en) * | 2010-12-23 | 2011-04-27 | 江西嘉柏新材料有限公司 | Method for recovering hydrogen gas from trichlorosilane tail gas |
| CN103170214A (en) * | 2013-04-15 | 2013-06-26 | 四川天一科技股份有限公司 | Method for recovering methane chloride from organic silicon synthetic tail gas |
| CN103170214B (en) * | 2013-04-15 | 2015-03-04 | 四川天一科技股份有限公司 | Method for recovering methane chloride from organic silicon synthetic tail gas |
| CN103588170A (en) * | 2013-11-15 | 2014-02-19 | 新特能源股份有限公司 | Treatment process for purifying recycled hydrogen during production of electronic-grade polycrystalline silicon |
| CN104556042A (en) * | 2014-12-29 | 2015-04-29 | 新疆大全新能源有限公司 | Polycrystalline silicon production method and equipment based on improved Siemens method |
| CN105169889A (en) * | 2015-10-26 | 2015-12-23 | 四川天一科技股份有限公司 | Pressure swing adsorption process for cascade purging |
| CN109790020A (en) * | 2016-09-26 | 2019-05-21 | 住友精化株式会社 | The refining methd and hydrogen of hydrogen or helium or the refining plant of helium |
| CN107344058A (en) * | 2017-09-08 | 2017-11-14 | 成都盛利达科技有限公司 | A kind of hydrogen chloride gas advanced purification process of energy-conservation |
| CN107344058B (en) * | 2017-09-08 | 2023-05-26 | 成都盛利达科技有限公司 | Energy-saving hydrogen chloride gas deep purification process |
| CN110550605A (en) * | 2018-06-04 | 2019-12-10 | 国家能源投资集团有限责任公司 | Device and method for preparing high-purity hydrogen from hydrogen-containing gas |
| CN110550605B (en) * | 2018-06-04 | 2021-06-11 | 国家能源投资集团有限责任公司 | Device and method for preparing high-purity hydrogen from hydrogen-containing gas |
| CN108926960A (en) * | 2018-08-31 | 2018-12-04 | 四川永祥新能源有限公司 | A kind of processing method of cold hydrogenated tail gas |
| CN109529534A (en) * | 2018-12-27 | 2019-03-29 | 四川天科技股份有限公司 | A kind of method and device for purifying organosilicon fractionation tail gas and recycling organic silicon monomer |
| CN109529534B (en) * | 2018-12-27 | 2021-05-04 | 西南化工研究设计院有限公司 | Method and device for purifying organic silicon fractionation tail gas and recycling organic silicon monomers |
| CN110639328A (en) * | 2019-09-16 | 2020-01-03 | 新疆大全新能源股份有限公司 | Method for removing trace carbon impurities in tail gas recovery hydrogen treatment process |
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Application publication date: 20100616 |