CN105036081A - Method for producing HCl gas through chlorosilane residual liquor - Google Patents
Method for producing HCl gas through chlorosilane residual liquor Download PDFInfo
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- CN105036081A CN105036081A CN201510467054.3A CN201510467054A CN105036081A CN 105036081 A CN105036081 A CN 105036081A CN 201510467054 A CN201510467054 A CN 201510467054A CN 105036081 A CN105036081 A CN 105036081A
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- hydrochloric acid
- absorption
- storage tank
- dilute hydrochloric
- stirred autoclave
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- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000005046 Chlorosilane Substances 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 173
- 238000010521 absorption reaction Methods 0.000 claims abstract description 77
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 15
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000005052 trichlorosilane Substances 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 238000003860 storage Methods 0.000 claims description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 44
- 239000003795 chemical substances by application Substances 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 235000013312 flour Nutrition 0.000 claims description 10
- 229910001510 metal chloride Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 230000018044 dehydration Effects 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 239000007921 spray Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 abstract description 53
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 38
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 38
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000460 chlorine Substances 0.000 abstract description 14
- 229910052801 chlorine Inorganic materials 0.000 abstract description 14
- 229910021420 polycrystalline silicon Inorganic materials 0.000 abstract description 6
- 230000007062 hydrolysis Effects 0.000 abstract description 5
- 239000010865 sewage Substances 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract 3
- 239000006096 absorbing agent Substances 0.000 abstract 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 229910003910 SiCl4 Inorganic materials 0.000 abstract 1
- 229910003818 SiH2Cl2 Inorganic materials 0.000 abstract 1
- 229910003822 SiHCl3 Inorganic materials 0.000 abstract 1
- 238000003795 desorption Methods 0.000 abstract 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 229920005591 polysilicon Polymers 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910003902 SiCl 4 Inorganic materials 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- QRZLYGZLLCROQC-UHFFFAOYSA-N [Na].[Cl].[Ca] Chemical compound [Na].[Cl].[Ca] QRZLYGZLLCROQC-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 229910004762 CaSiO Inorganic materials 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 108091006629 SLC13A2 Proteins 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Silicon Compounds (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method for producing HCl gas through chlorosilane residual liquor, and belongs to the field of recycling chlorosilane residual liquor in the polycrystalline silicon industry. The mode that a stirring reaction kettle and an absorption tower are connected for use is adopted, the chlorosilane residual liquor is hydrolyzed in the stirring reaction kettle, and after H2 and HCl gas generated through hydrolysis of the residual liquor and SiCl4, SiHCl3 and SiH2Cl2 volatile gas which is not reacted completely are fully absorbed by the absorption tower, more than 99% of chlorine is absorbed in the way of hydrogen chloride; tail gas is alkali-washed and then is discharged with the standard level; absorption liquid of the absorption tower enters the stirring reaction kettle to serve as a residual liquor hydrolysis reaction absorbing agent, the HCl gas generated by desorption of concentrated hydrochloric acid can return to the trichlorosilane synthesis process, desorbed diluted hydrochloric acid serves as the absorbing agent of the system, and therefore chlorine can be recycled. By the adoption of the method, chlorine in the chlorosilane residual liquor is effectively recycled, resource utilization is achieved, the quantity of chloride ions entering a follow-up sewage treatment device is reduced, and the treatment cost of factory sewage is lowered.
Description
Technical field
The present invention relates to a kind of method that chlorosilane raffinate produces HCl gas, belong to polysilicon industry chlorosilane raffinate resource utilization field.
Background technology
In recent years, the situation in short supply of Nonrenewable energy resources and the fast developments of photovoltaic industry such as oil, coal, electric power, promoted the development of polysilicon industry greatly.Current domestic polysilicon industry many employings improved Siemens, the i.e. closed loop hydrogen reduction of trichlorosilane, but because the United Technologies of U.S., day, De Deng developed country are blocked, domesticly do not grasp improved Siemens completely, cannot realize loop production, therefore a large amount of materials becomes chlorosilane raffinate and waste gas.
Chlorosilane raffinate main source: the synthesis procedure of trichlorosilane, the rectification and purification operation of trichlorosilane, the reduction operation of trichlorosilane.
The main component of chlorosilane raffinate: SiCl
4, SiHCl
3, SiH
2cl
2, HCl, a small amount of silica flour and metal chloride;
Current domestic polysilicon factory raffinate process major part adopts in alkali lye and technique, and mainly because its investment is less, technical process is simple, can realize the harmlessness disposing of chlorosilane raffinate.Technique is roughly: the chlorosilane raffinate produced in production of polysilicon directly enters alkali lye (NaOH or Ca (OH)
2solution) eluting column, generate NaC1, CaCl
2, SiO
2, Na
2siO
3, CaSiO
3deng, tail gas is (containing H
2, other rare gas elementes) and emptying, liquid phase then delivers to follow-up treatment unit for waste water, and carry out filtration and evaporation mode desalination and solid waste disposal, the solid waste of formation carries out storing up or landfill disposal, and waste water discharges after carrying out advanced treatment.
Base extraction technique only achieves the harmlessness disposing of chlorosilane raffinate, and the useful matter such as water glass (calcium), silicon-dioxide, sodium-chlor (calcium) generated is recycled, and causes the wasting of resources.Secondly, using alkali lye as absorption agent, due to the stickiness of alkali lye and silicate, cause line clogging serious, and in absorption liquid collecting tank and circulatory pool, have a large amount of throw outs produce, pond bear building-up block, not easy to clean.
Chlorosilane raffinate is different from simple silicon tetrachloride, and the hydrolysis of chlorosilane raffinate can produce a large amount of H
2, so different from the treatment process of silicon tetrachloride, can not carry out in unlimited system, the firing property of hydrogen need be considered, need carry out in airtight system, and by a large amount of H of hydrolyzing chlorosilane generation
2timely safety is drained.
Chlorosilane raffinate produces a method for HCl gas, adopts the mode that stirred autoclave and absorption tower are used in conjunction, and system adopts atmospheric unit, and stirred autoclave hydrolysis reaction produces H
2, HCl gas and unreacted SiCl completely
4, SiHCl
3, SiH
2cl
2volatile gases, enters after absorption tower is again fully hydrolyzed by service water and circulation dilute hydrochloric acid and absorbs, qualified discharge after tail gas alkaline cleaning operation absorbs; The method is except make up water, do not introduce other elements, the chlorine element in chlorosilane raffinate is made to be converted into HCl completely, and hydrolyzing chlorosilane reaction carries out in acid condition, effective minimizing silicate generates, make the separating-purifying of the hydrochloric acid of subsequent process and hydrogenchloride easier, the HCl gas of acquisition is more pure; Present invention achieves the chlorine in chlorosilane raffinate to reclaim with the form of hydrogenchloride, the concentrated hydrochloric acid obtained resolves the synthesis procedure that the HCl gas produced can get back to trichlorosilane, achieve the resource circulation utilization of chlorine element, and the dilute hydrochloric acid after resolving is got back in chlorosilane raffinate hydrolysis system as absorption agent, reduce the amount entering the chlorion of follow-up waste disposal plant, reduce subsequent wastewater treatment cost.
Summary of the invention
In chlorosilane raffinate, main component is SiCl
4, SiHCl
3, SiH
2cl
2and HCl, containing a large amount of chlorine elements in visible raffinate, traditional raffinate treatment process, not only consume a large amount of alkali, the sodium-chlor (calcium) formed, water glass (calcium) and silica mixture, separation difficulty, causes the chlorine wasting of resources, create a large amount of sodium-chlor (calcium), water glass (calcium) solution, make follow-up waste water treatmentntrol difficult, cost high.
A kind of chlorosilane raffinate is the object of the present invention is to provide to produce the method for HCl gas, realize chlorine element in chlorosilane raffinate to reclaim with the form of HCl gas, and get back to through deep purifying in the synthesis procedure of trichlorosilane and go, the resource recycling realizing chlorine element utilizes, also alleviate follow-up treatment pressure of sewage, reduce factory's environmental protection cost, specifically comprise the following steps:
(1) the chlorosilane raffinate removing most of silica flour and metal chloride through sedimentation and filtration is transported to raffinate storage tank 1, uses N
2chlorosilane raffinate is pressed onto from raffinate storage tank 1 the absorption liquid generation hydrolysis reaction that stirred autoclave 2 gets off with absorption tower 3, and reaction time is 5 ~ 10 minutes.
(2) in absorption tower 3, absorb the volatilization gas of stirred autoclave 2 generation with dilute hydrochloric acid, absorption liquid then enters stirred autoclave 2, and tail gas is qualified discharge after tail gas alkaline cleaning operation absorbs.
(3) stirred autoclave 2 reaction solution is sent into filter 4 and filter out silica solid, after filtering, gained filtrate is concentrated hydrochloric acid, enters concentrated hydrochloric acid storage tank 5.
(4) silica solid filter residue service water washs, and washings is dilute hydrochloric acid, enters washings storage tank 6, and this washings, absorbs from absorption tower 3 top spray stirred autoclave 2 Volatile Gas further as absorption agent.
(5) concentrated hydrochloric acid of acquisition is delivered to resolving hydrochloric acid tower 7 to resolve, obtain HCl gas, the dilute hydrochloric acid after parsing enters dilute hydrochloric acid storage tank 8.
(6) concentrated hydrochloric acid in dilute hydrochloric acid in dilute hydrochloric acid storage tank 8 and concentrated hydrochloric acid storage tank 5 is mixed with the dilute hydrochloric acid that mass percent concentration is 25 ~ 28% in absorption agent Preparation tank 9, after interchanger 10 cools, enter in absorption tower 3, Volatile Gas that bottom produces as absorption agent cyclic absorption stirred autoclave 2.
(7) HCl gas enters trichlorosilane synthesis process system after deep cooling dehydration.
The main component of described chlorosilane raffinate is 30 ~ 95%(mass percent concentration, not dated especially, and all concentration of the present invention is mass percent concentration) SiCl
4, 3 ~ 40% SiHCl
3, 1 ~ 25% SiH
2cl
2, 0.5 ~ 5%HCl, a small amount of silica flour and metal chloride.
Preferably, the temperature of stirred autoclave 2 of the present invention is less than 50 DEG C.
Preferably, washings temperature of the present invention controls at 10 ~ 30 DEG C, and absorption agent Preparation tank 9 dilute hydrochloric acid interchanger 10 is out cooled to 10 ~ 30 DEG C.
Preferably, the dilute hydrochloric acid concentration made in absorption agent Preparation tank 9 of the present invention is 25 ~ 28%.
The concentration of the HCl gas of described acquisition is 93 ~ 99%.
Beneficial effect of the present invention:
(1) the present invention's mode of adopting stirred autoclave and absorption tower to be used in conjunction to be hydrolyzed absorption to chlorosilane raffinate, in stirred autoclave, chlorosilane raffinate and dilute hydrochloric acid carry out liquid liquid hydrolysis reaction, the chlorosilane gas volatilized in absorption tower and dilute hydrochloric acid carry out gas-liquid hydrolysis reaction, ensure liquid and gas chlorosilane abundant hydrolysis reaction all in acid condition, prevent the generation of silicate, be convenient to follow-up filtering separation and the parsing of HCl, simultaneously, adopt eluting column atmospheric unit, make the H that hydrolysis produces
2can discharge safely in time.
(2) concentrated hydrochloric acid that the hydrolysis of chlorosilane raffinate produces resolves the synthesis procedure that the HCl gas produced can get back to trichlorosilane, and the absorption agent that the dilute hydrochloric acid after parsing is hydrolyzed as chlorosilane raffinate, realizes the recycle of chlorine element in raffinate.
(3) the present invention is using water and dilute hydrochloric acid as absorption agent, avoid the introducing of other elements, the chlorine element in chlorosilane raffinate is made to be converted into HCl completely, and hydrolyzing chlorosilane reaction carries out in acid condition, effective minimizing silicate generates, make the separating-purifying of the hydrochloric acid of subsequent process and hydrogenchloride easier, the HCl gas of acquisition is more pure.
(4) the present invention has reclaimed most chlorine element and recycling, reduces the amount entering into the chlorine element of subsequent wastewater treatment operation, thus alleviates follow-up treatment pressure of sewage, reduces factory's environmental protection cost.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
In figure: 1-chlorosilane raffinate storage tank, 2-stirred autoclave, 3-absorption tower, 4-filter, 5-concentrated hydrochloric acid storage tank, 6-washings storage tank, 7-resolving hydrochloric acid tower, 8-dilute hydrochloric acid storage tank, 9-absorption agent Preparation tank, 10-interchanger.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
The embodiment of the present invention 1 ~ 3 device used as shown in Figure 1, comprise chlorosilane raffinate storage tank 1, stirred autoclave 2, absorption tower 3, filter 4, concentrated hydrochloric acid storage tank 5, washings storage tank 6, resolving hydrochloric acid tower 7, dilute hydrochloric acid storage tank 8, absorption agent Preparation tank 9, interchanger 10.Chlorosilane raffinate storage tank 1 is communicated with stirred autoclave 2, stirred autoclave 2 and absorption tower 3 are by two pipeline connections, stirred autoclave 2 is communicated with filter 4 by pump, filter 4 is communicated with concentrated hydrochloric acid storage tank 5, filter 4 is communicated with washings storage tank 6, washings storage tank 6 is communicated with absorption tower 3 by pump, concentrated hydrochloric acid storage tank 5 is communicated with resolving hydrochloric acid tower 7 by pump, resolving hydrochloric acid tower 7 is communicated with dilute hydrochloric acid storage tank 8, concentrated hydrochloric acid storage tank 5 is communicated with absorption agent Preparation tank 9 by pump with dilute hydrochloric acid storage tank 8, absorption agent Preparation tank 9 is communicated with interchanger 10 by pump, interchanger 10 is communicated with absorption tower 3.
Embodiment 1
Described in the present embodiment, a kind of chlorosilane raffinate produces the method for HCl gas, it is characterized in that, comprises the following steps:
The main component of the chlorosilane raffinate of the present embodiment process is the SiCl of 40%
4, 40% SiHCl
3, 15% SiH
2cl
2, 5%HCl, a small amount of silica flour and metal chloride, treatment capacity is 0.5t/h.
(1) the chlorosilane raffinate removing most of silica flour and metal chloride through sedimentation and filtration is transported to raffinate storage tank 1, uses N
2chlorosilane raffinate is pressed onto from raffinate storage tank 1 the absorption liquid generation hydrolysis reaction that stirred autoclave 2 gets off with absorption tower 3, and reaction time is 6 minutes, and controlling stirred autoclave 2 temperature is 45 ~ 50 DEG C.
(2) in absorption tower 3, absorb the volatilization gas of stirred autoclave 2 generation with dilute hydrochloric acid, absorption liquid then enters tail gas qualified discharge after tail gas alkaline cleaning operation absorbs of stirred autoclave 2,10kg/h.
(3) stirred autoclave 2 reaction solution is sent into filter 4 and filter out silica solid, after filtering, gained filtrate is the concentrated hydrochloric acid of 29%, enters concentrated hydrochloric acid storage tank 5.
(4) silica solid filter residue 1200kg/h service water washs, and washings is the dilute hydrochloric acid of 18%, enters washings storage tank 6, and washings temperature controls about 25 DEG C.
(5) washings is as absorption agent from absorption tower 3 top spray, absorbs further stirred autoclave 2 Volatile Gas.
(6) concentrated hydrochloric acid of obtain 29% is delivered to resolving hydrochloric acid tower 7 to resolve, obtain the HCl gas of 93% of 315kg/h, the dilute hydrochloric acid of 21% after parsing enters dilute hydrochloric acid storage tank 8.
(7) dilute hydrochloric acid of 21% and the concentrated hydrochloric acid of 29% are mixed with in absorption agent Preparation tank 9 dilute hydrochloric acid of 25%, after interchanger 10 cools, enter in absorption tower 3, Volatile Gas that bottom produces as absorption agent cyclic absorption stirred autoclave 2, the dilute hydrochloric acid temperature of 25% after heat exchange controls about 25 DEG C.
(8) HCl gas enters trichlorosilane synthesis process system after deep cooling dehydration.
Embodiment 2
Described in the present embodiment, a kind of chlorosilane raffinate produces the method for HCl gas, it is characterized in that, comprises the following steps:
The main component of the chlorosilane raffinate of the present embodiment process is the SiCl of 60%
4, 30% SiHCl
3, 9% SiH
2cl
2, 1%HCl, a small amount of silica flour and metal chloride, treatment capacity 0.5t/h.
(1) the chlorosilane raffinate removing most of silica flour and metal chloride through sedimentation and filtration is transported to raffinate storage tank 1, uses N
2chlorosilane raffinate is pressed onto from raffinate storage tank 1 the absorption liquid generation hydrolysis reaction that stirred autoclave 2 gets off with absorption tower 3, and reaction time is 8 minutes, and controlling stirred autoclave 2 temperature is 40 ~ 45 DEG C.
(2) in absorption tower 3, absorb the volatilization gas of stirred autoclave 2 generation with dilute hydrochloric acid, absorption liquid then enters tail gas qualified discharge after tail gas alkaline cleaning operation absorbs of stirred autoclave 2,8.2kg/h.
(3) stirred autoclave 2 reaction solution is sent into filter 4 and filter out silica solid, after filtering, gained filtrate is the concentrated hydrochloric acid of 30%, enters concentrated hydrochloric acid storage tank 5.
(4) silica solid filter residue 1100kg/h service water washs, and washings is the dilute hydrochloric acid of 20%, enters washings storage tank 6, and washings temperature controls about 20 DEG C.
(5) washings is as absorption agent from absorption tower 3 top spray, absorbs further stirred autoclave 2 Volatile Gas.
(6) concentrated hydrochloric acid of obtain 30% is delivered to resolving hydrochloric acid tower 7 to resolve, obtain the HCl gas of 96% of 312kg/h, the dilute hydrochloric acid of 21% after parsing enters dilute hydrochloric acid storage tank 8.
(7) dilute hydrochloric acid of 21% and the concentrated hydrochloric acid of 30% are mixed with in absorption agent Preparation tank 9 dilute hydrochloric acid of 26%, after interchanger 10 cools, enter in absorption tower 3, Volatile Gas that bottom produces as absorption agent cyclic absorption stirred autoclave 2, the dilute hydrochloric acid temperature of 26% after heat exchange controls about 20 DEG C.
(8) HCl gas enters trichlorosilane synthesis process system after deep cooling dehydration.
Embodiment 3
Described in the present embodiment, a kind of chlorosilane raffinate produces the method for HCl gas, it is characterized in that, comprises the following steps:
The main component of the chlorosilane raffinate of the present embodiment process is the SiCl of 90%
4, 5% SiHCl
3, 4.5% SiH
2cl
2, 0.5%HCl, a small amount of silica flour and metal chloride, treatment capacity is 0.5t/h.
(1) the chlorosilane raffinate removing most of silica flour and metal chloride through sedimentation and filtration is transported to raffinate storage tank 1, uses N
2chlorosilane raffinate is pressed onto from raffinate storage tank 1 the absorption liquid generation hydrolysis reaction that stirred autoclave 2 gets off with absorption tower 3, and reaction time is 10 minutes, and controlling stirred autoclave 2 temperature is 35 ~ 40 DEG C.
(2) in absorption tower 3, absorb the volatilization gas of stirred autoclave 2 generation with dilute hydrochloric acid, absorption liquid then enters tail gas qualified discharge after tail gas alkaline cleaning operation absorbs of stirred autoclave 2,5.5kg/h.
(3) stirred autoclave 2 reaction solution is sent into filter 4 and filter out silica solid, after filtering, gained filtrate is the concentrated hydrochloric acid of 31%, enters concentrated hydrochloric acid storage tank 5.
(4) silica solid filter residue 1000kg/h service water washs, and washings is the dilute hydrochloric acid of 20%, enters washings storage tank 6, and washings temperature controls about 15 DEG C.
(5) washings is as absorption agent from absorption tower 3 top spray, absorbs further stirred autoclave 2 Volatile Gas.
(6) concentrated hydrochloric acid of obtain 31% is delivered to resolving hydrochloric acid tower 7 to resolve, obtain the HCl gas of 98% of 324kg/h, the dilute hydrochloric acid of 19% after parsing enters dilute hydrochloric acid storage tank 8.
(7) dilute hydrochloric acid of 19% and the concentrated hydrochloric acid of 31% are mixed with in absorption agent Preparation tank 9 dilute hydrochloric acid of 27%, after interchanger 10 cools, enter in absorption tower 3, Volatile Gas that bottom produces as absorption agent cyclic absorption stirred autoclave 2, the dilute hydrochloric acid temperature of 27% after heat exchange controls about 15 DEG C.
(8) HCl gas enters trichlorosilane synthesis process system after deep cooling dehydration.
Claims (3)
1. chlorosilane raffinate produces a method for HCl gas, it is characterized in that, comprises the following steps:
(1) the chlorosilane raffinate removing most of silica flour and metal chloride through sedimentation and filtration is transported in raffinate storage tank (1), uses N
2chlorosilane raffinate is pressed onto absorption liquid generation hydrolysis reaction stirred autoclave (2) and absorption tower (3) got off from raffinate storage tank (1), reaction time is 5 ~ 10 minutes;
(2) with the dilute hydrochloric acid volatilization gas that absorption stirred autoclave (2) produces in absorption tower (3), absorption liquid then enters stirred autoclave (2), and tail gas is qualified discharge after tail gas alkaline cleaning operation absorbs;
(3) stirred autoclave (2) reaction solution is sent into filter (4) and filter out silica solid, after filtering, gained filtrate is concentrated hydrochloric acid, enters concentrated hydrochloric acid storage tank (5);
(4) silica solid filter residue service water washs, and washings is dilute hydrochloric acid, enters washings storage tank (6), and this washings, absorbs from absorption tower (3) top spray stirred autoclave (2) Volatile Gas further as absorption agent;
(5) concentrated hydrochloric acid of acquisition is delivered to resolving hydrochloric acid tower (7) to resolve, obtain HCl gas, the dilute hydrochloric acid after parsing enters dilute hydrochloric acid storage tank (8);
(6) concentrated hydrochloric acid in dilute hydrochloric acid in dilute hydrochloric acid storage tank (8) and concentrated hydrochloric acid storage tank (5) is mixed with the dilute hydrochloric acid that mass percent concentration is 25 ~ 28% in absorption agent Preparation tank (9), after interchanger (10) cooling, enter in absorption tower (3), Volatile Gas that bottom produces as absorption agent cyclic absorption stirred autoclave (2);
(7) HCl gas enters trichlorosilane synthesis process system after deep cooling dehydration.
2. a kind of chlorosilane raffinate according to claim 1 produces the method for HCl gas, it is characterized in that: the temperature of stirred autoclave (2) is less than 50 DEG C.
3. a kind of chlorosilane raffinate according to claim 1 produces the method for HCl gas, and it is characterized in that: washings temperature controls at 10 ~ 30 DEG C, absorption agent Preparation tank (9) dilute hydrochloric acid interchanger (10) is out cooled to 10 ~ 30 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510467054.3A CN105036081B (en) | 2015-08-03 | 2015-08-03 | A kind of method that chlorosilane raffinate produces HCl gases |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510467054.3A CN105036081B (en) | 2015-08-03 | 2015-08-03 | A kind of method that chlorosilane raffinate produces HCl gases |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105036081A true CN105036081A (en) | 2015-11-11 |
| CN105036081B CN105036081B (en) | 2017-06-13 |
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| CN105668518A (en) * | 2016-01-11 | 2016-06-15 | 昆明冶研新材料股份有限公司 | Treatment method and system for chlorosilane residual gas-liquid mixture |
| CN106006557A (en) * | 2016-05-18 | 2016-10-12 | 昆明理工大学 | Method for producing hydrogen chloride from chlorosilane raffinate |
| CN106276924A (en) * | 2016-08-22 | 2017-01-04 | 昆明理工大学 | A kind of process chlorosilane residual liquid and the method for waste gas simultaneously |
| CN107789966A (en) * | 2017-11-21 | 2018-03-13 | 南京钟腾化工有限公司 | The recovery system and method for tail gas in a kind of chlorination toluene production |
| CN107804852A (en) * | 2016-09-08 | 2018-03-16 | 新特能源股份有限公司 | Prepare the method and system of aerosil |
| CN108525469A (en) * | 2018-05-25 | 2018-09-14 | 南通鑫宝石墨设备有限公司 | The processing system and its processing method of tail gas in a kind of Production of PVC |
| CN111717892A (en) * | 2020-07-30 | 2020-09-29 | 青岛东正环保科技有限公司 | Method for preparing high-purity high-concentration hydrochloric acid by hydrothermal hydrolysis of organic silicon high-boiling residues |
| CN112321626A (en) * | 2020-11-10 | 2021-02-05 | 云南能投硅材科技发展有限公司 | Method for treating organic silicon slag slurry |
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| CN105668518A (en) * | 2016-01-11 | 2016-06-15 | 昆明冶研新材料股份有限公司 | Treatment method and system for chlorosilane residual gas-liquid mixture |
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| CN106276924A (en) * | 2016-08-22 | 2017-01-04 | 昆明理工大学 | A kind of process chlorosilane residual liquid and the method for waste gas simultaneously |
| CN107804852A (en) * | 2016-09-08 | 2018-03-16 | 新特能源股份有限公司 | Prepare the method and system of aerosil |
| CN107804852B (en) * | 2016-09-08 | 2019-12-06 | 新特能源股份有限公司 | Method and system for preparing silicon dioxide aerogel |
| CN107789966A (en) * | 2017-11-21 | 2018-03-13 | 南京钟腾化工有限公司 | The recovery system and method for tail gas in a kind of chlorination toluene production |
| CN108525469A (en) * | 2018-05-25 | 2018-09-14 | 南通鑫宝石墨设备有限公司 | The processing system and its processing method of tail gas in a kind of Production of PVC |
| CN108525469B (en) * | 2018-05-25 | 2023-09-19 | 南通鑫宝石墨设备有限公司 | Tail gas treatment system and method in polyvinyl chloride production |
| CN111717892A (en) * | 2020-07-30 | 2020-09-29 | 青岛东正环保科技有限公司 | Method for preparing high-purity high-concentration hydrochloric acid by hydrothermal hydrolysis of organic silicon high-boiling residues |
| CN112321626A (en) * | 2020-11-10 | 2021-02-05 | 云南能投硅材科技发展有限公司 | Method for treating organic silicon slag slurry |
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