CN110294458A - A kind of method and apparatus that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online - Google Patents
A kind of method and apparatus that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online Download PDFInfo
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- CN110294458A CN110294458A CN201910480703.1A CN201910480703A CN110294458A CN 110294458 A CN110294458 A CN 110294458A CN 201910480703 A CN201910480703 A CN 201910480703A CN 110294458 A CN110294458 A CN 110294458A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/1487—Removing organic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/14—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/07—Purification ; Separation
- C01B7/0706—Purification ; Separation of hydrogen chloride
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Abstract
The invention discloses the method and apparatus that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online, method is that the synthesis tail gas of alkyl dichloride phosphine is successively carried out to the absorption of the primary cycle using soft water as initial absorption solvent, secondary cycle absorption and three-level cyclic absorption, and absorbing liquids at different levels are periodically discharged and supplements lyosoption and exhaust gas is discharged after three-level cyclic absorption.Equipment includes primary cycle absorptive unit, secondary cycle absorptive unit and the three-level cyclic absorption unit being connected in series.The present invention selects suitable lyosoption and utilizes reactive absorption phosphorus containg substances, recycle hydrogen chloride gas and the relative volatility difference of phosphorus containg substances solution soluble in water and the difference of solubility, it solves the separation problem of phosphorus containg substances and hydrogen chloride, realizes the purpose that by-product hydrogen chloride gas is prepared into technical-grade hydrochloric acid resource utilization.
Description
Technical field
The invention belongs to the technical fields of chemical synthesis resource utilization, more particularly, are related to a kind of alkyl dichloride
The method and apparatus that phosphine synthesis by-product hydrogen chloride purifies online.
Background technique
With the fast development of Chinese economy, increasing rapidly in agricultural and industrial production to the demand of organic phosphorus compound
It is long.Alkyl phosphorus dichloride is the important intermediate of organic phosphorus compound synthesis, and purposes is extremely wide, can be with by alkyl dichloride phosphine
Hundreds of organic phosphorus compound is directly or indirectly synthesized, and the reaction conversion ratio using it as starting material is high, it is most anti-
It should nearly all be quantitative carry out.
Alkyl phosphorus dichloride can be synthesized by phosphorus trichloride with corresponding alkyl, and reaction needs to carry out at high temperature, this is anti-
The byproduct hydrogen chloride and a small amount of phosphorus containg substances for answering generation will be by that will generate a large amount of phosphorous high-salt wastewater, place after absorbing by liquid caustic soda
Reason difficulty and higher cost.With the development of environmentally protective chemistry, how to realize that the purifying of hydrogen chloride and resource utilization become
The major issue of the technique.
It discloses in the prior art and sodium chloride waste water is generated by scrubbing tower cyclic absorption using dilute sodium hydroxide solution,
But there are periodic detection absorbing liquid pH value, periodic replacement liquid alkaline, generate a large amount of phosphorous high-salt wastewater, three-protection design it is difficult and at
The disadvantages of this is higher.
Summary of the invention
In order to solve the problems in the existing technology, the object of the present invention is to provide a kind of synthesis of alkyl dichloride phosphine is secondary
The method and apparatus that hydrogen chloride purifies online is produced, suitable lyosoption is selected and utilizes reactive absorption phosphorus containg substances, is recycled
Hydrogen chloride gas and the relative volatility difference of phosphorus containg substances solution soluble in water and the difference of solubility, solve phosphorus containg substances
With the separation problem of hydrogen chloride, the purpose that by-product hydrogen chloride gas is prepared into technical-grade hydrochloric acid resource utilization is realized.
An aspect of of the present present invention provides the method that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online, by alkyl two
The synthesis tail gas of phosphonium chloride successively carries out the absorption of the primary cycle using soft water as initial absorption solvent, secondary cycle absorption and three
Grade cyclic absorption, is periodically discharged absorbing liquids at different levels and supplements lyosoption and exhaust gas is discharged after three-level cyclic absorption, wherein
The first order absorption liquid of discharge is phosphorous sour water, and the second level absorbing liquid of discharge is technical-grade hydrochloric acid.
The one embodiment for the method that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to the present invention, the alkane
Base dichloride phosphine is dichloromethylphosphine or ethyl dichloride phosphine, the phosphorus containg substances in the synthesis tail gas include phosphorus trichloride and
The alkyl dichloride phosphine.
One embodiment for the method that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to the present invention, when described
It is discharged when total phosphorus content reaches 100g/L~250g/L in the first order absorption liquid that primary cycle absorbs as phosphorous sour water, wherein
Total phosphorus content is preferably 150g/L~250g/L in the first order absorption liquid, particularly preferably 200g/L~250g/L.
One embodiment for the method that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to the present invention, when described
It is discharged when HCl mass concentration is 31~35% in the second level absorbing liquid that secondary cycle absorbs as technical-grade hydrochloric acid, wherein second level
HCl mass concentration is preferably 32~34% in absorbing liquid.
One embodiment for the method that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to the present invention, by three-level
The three-level absorbing liquid of cyclic absorption discharge is supplemented to secondary cycle as the lyosoption that secondary cycle absorbs and absorbs, and soft water is made
It is absorbed for primary cycle and the lyosoption of three-level cyclic absorption is supplemented to primary cycle and absorbs and three-level cyclic absorption.
Another aspect provides the equipment that a kind of alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online, institutes
Stating equipment includes primary cycle absorptive unit, secondary cycle absorptive unit and the three-level cyclic absorption unit being connected in series, described
The air inlet of primary cycle absorptive unit is connected with the synthesis tail gas supply source of alkyl dichloride phosphine, primary cycle absorptive unit
Gas outlet is connected with the air inlet of secondary cycle absorptive unit and the gas outlet of secondary cycle absorptive unit and three-level cyclic absorption
The air inlet of unit is connected, and the gas outlet of three-level cyclic absorption unit is connected with atmosphere or exhaust gas treatment unit.
The one embodiment for the equipment that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to the present invention, described one
Grade cyclic absorption unit includes first order absorption cooler, first order absorption storage tank and first order absorption circulating pump, and the first order absorption is cold
But the air inlet of device is connected and the discharge port and level-one of first order absorption cooler with the synthesis tail gas supply source of alkyl dichloride phosphine
The feed inlet for absorbing storage tank is connected, and the inlet of first order absorption storage tank is connected with soft water supply source and liquid outlet passes through first order absorption
Circulating pump and primary cycle pipe are connected with the inlet of first order absorption cooler, are provided with first order absorption on the primary cycle pipe
Liquid outlet.
The one embodiment for the equipment that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to the present invention, described two
Grade cyclic absorption unit includes second level tail gas absorber and second level absorbent recirculation pump, the air inlet of the second level tail gas absorber with
The gas outlet of primary cycle absorptive unit is connected, and the first inlet of second level tail gas absorber is connected with soft water supply source and second level
The liquid outlet of tail gas absorber lower part pass through second level absorbent recirculation pump and secondary cycle pipe and second level tail gas absorber top the
Two inlets are connected, and second level absorbing liquid outlet is provided on the secondary cycle pipe.
The one embodiment for the equipment that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to the present invention, described three
Grade cyclic absorption unit includes three-level tail gas absorber and three-level absorbent recirculation pump, the air inlet of the three-level tail gas absorber with
The gas outlet of secondary cycle absorptive unit is connected, and the first inlet of three-level tail gas absorber is connected with soft water supply source and three-level
The liquid outlet of tail gas absorber lower part pass through three-level absorbent recirculation pump and three-level circulation pipe and three-level tail gas absorber top the
Two inlets are connected, and three-level absorbing liquid outlet is provided on the three-level circulation pipe.
The one embodiment for the equipment that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to the present invention, described two
First inlet of grade tail gas absorber also passes through recurrent canal and is connected with the three-level absorbing liquid outlet.
Compared with prior art, the method and apparatus energy that alkyl dichloride phosphine synthesis by-product hydrogen chloride of the present invention purifies online
It enough avoids the consumption of liquid alkaline and reduces the cost of raw material, avoid the generation of phosphorous high-salt wastewater, phosphorus containg substances removal rate reaches
99.9%, reduce the processing cost of the three wastes；The recycling for realizing by-product hydrogen chloride gas 98% simultaneously, has been made technical grade
Hydrochloric acid byproduct.
Detailed description of the invention
Fig. 1 shows what alkyl dichloride phosphine synthesis by-product hydrogen chloride according to an exemplary embodiment of the present invention purified online
The structural schematic diagram of equipment.
Description of symbols:
10- primary cycle absorptive unit, 11- first order absorption cooler, 12- first order absorption storage tank, 13- first order absorption circulation
Pump, 14- primary cycle pipe, 15- first order absorption liquid outlet, the inlet of 16- first order absorption storage tank, 20- secondary cycle absorb
Unit, 21- second level tail gas absorber, 22- second level absorbent recirculation pump, 23- secondary cycle pipe, 24- second level absorbing liquid outlet,
First inlet of 25- second level tail gas absorber, the second inlet of 26- second level tail gas absorber, 30- three-level cyclic absorption list
Member, 31- three-level tail gas absorber, 32- three-level absorbent recirculation pump, 33- three-level circulation pipe, 34- three-level absorbing liquid outlet, 35-
First inlet of three-level tail gas absorber, the second inlet of 36- three-level tail gas absorber, 37- recurrent canal.
Specific embodiment
All features disclosed in this specification or disclosed all processing methods or in the process the step of, in addition to mutual
Other than the feature and/or step of repulsion, it can combine in any way.
Any feature disclosed in this specification unless specifically stated can be equivalent or with similar purpose by other
Alternative features are replaced.That is, unless specifically stated, each feature is an example in a series of equivalent or similar characteristics
?.
The method and apparatus purified online to alkyl dichloride phosphine of the present invention synthesis by-product hydrogen chloride is carried out respectively below
It is described in detail.
An exemplary embodiment of the present invention, the method that the alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online
It is that the synthesis tail gas of alkyl dichloride phosphine successively carries out to primary cycle using soft water as initial absorption solvent absorbs, second level is followed
Ring absorbs and three-level cyclic absorption, and absorbing liquids at different levels are periodically discharged and supplements lyosoption and is discharged after three-level cyclic absorption
Exhaust gas, wherein the first order absorption liquid of discharge is phosphorous sour water, and the second level absorbing liquid of discharge is technical-grade hydrochloric acid.
That is, the present invention recycles synthesis tail by selecting suitable lyosoption and utilizing reactive absorption phosphorus containg substances
Hydrogen chloride gas and the relative volatility difference of phosphorus containg substances solution soluble in water and the difference of solubility in gas, solve and contain
The separation problem of phosphorus substance and hydrogen chloride realizes the mesh that by-product hydrogen chloride gas is prepared into technical-grade hydrochloric acid resource utilization
's.
Wherein, the synthesis tail gas of alkyl dichloride phosphine is by phosphorus trichloride and corresponding alkyl synthesis of alkyl two in the present invention
The synthesis tail gas generated when phosphonium chloride, including hydrogen chloride and a small amount of phosphorus containg substances.Soft water in the present invention refer to be free of or
Water containing less solubility calcium, magnesium compound.
Specifically, abovementioned alkyl dichloride phosphine can be dichloromethylphosphine or ethyl dichloride phosphine, in synthesis tail gas
Phosphorus containg substances include phosphorus trichloride and alkyl dichloride phosphine.
Primary cycle, which absorbs mainly to react using soft water with phosphorus containg substances, achievees the purpose that cyclic absorption phosphorus containg substances, when one
It is discharged when total phosphorus content reaches 100g/L~250g/L in the first order absorption liquid of grade cyclic absorption as phosphorous sour water.When total phosphorus contains
When measuring excessively high, the phosphorus containg substances removal rate that primary cycle absorbs will decline, and lead to the reduction of hydrogen chloride resource rate.Wherein, one
Total phosphorus content is preferably 150g/L~250g/L in grade absorbing liquid, particularly preferably 200g/L~250g/L.
Secondary cycle, which absorbs, mainly reaches purifying and by-product chlorination using soft water or three-level absorbing liquid circularly absorbing hydrogen chloride
The resource utilization purpose of hydrogen is made when HCl mass concentration is 31~35% in the second level absorbing liquid that secondary cycle absorbs
For technical-grade hydrochloric acid discharge.Wherein, HCl mass concentration is preferably 32~34% in second level absorbing liquid.
Three-level cyclic absorption mainly utilizes soft water to supplement circularly absorbing hydrogen chloride gas, further decreases the chlorination in tail gas
Hydrogen content, further recycling hydrogen chloride gas.
In accordance with the present invention it is preferred that the absorption that the three-level absorbing liquid that three-level cyclic absorption is discharged is absorbed as secondary cycle
Solvent make-up to secondary cycle absorbs, and soft water is absorbed as primary cycle and is supplemented with the lyosoption of three-level cyclic absorption
It is absorbed and three-level cyclic absorption to primary cycle.
By the above method, the phosphorus containg substances in synthesis tail gas can be separated with hydrogen chloride gas and by hydrogen chloride gas
Recycling is prepared into technical-grade hydrochloric acid, realizes purifying and resource utilization.
Another aspect provides the equipment that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online, the equipment
Combined with above use has more preferably technical effect.
Fig. 1 shows what alkyl dichloride phosphine synthesis by-product hydrogen chloride according to an exemplary embodiment of the present invention purified online
The structural schematic diagram of equipment.
As shown in Figure 1, an exemplary embodiment of the present invention, the equipment includes that the primary cycle being connected in series absorbs
Unit 10, secondary cycle absorptive unit 20 and three-level cyclic absorption unit 30, primary cycle absorptive unit 10 is for carrying out level-one
Cyclic absorption, secondary cycle absorptive unit 20 is for carrying out secondary cycle absorption, and three-level cyclic absorption unit 30 is for carrying out three
Grade cyclic absorption.
Wherein, the air inlet of primary cycle absorptive unit 10 is connected with the synthesis tail gas supply source of alkyl dichloride phosphine, and one
The gas outlet of grade cyclic absorption unit 10 is connected with the air inlet of secondary cycle absorptive unit 20 and secondary cycle absorptive unit 20
Gas outlet be connected with the air inlet of three-level cyclic absorption unit 30, the gas outlet of three-level cyclic absorption unit 30 and atmosphere or useless
Gas disposal unit is connected.
Specifically, primary cycle absorptive unit 10 of the invention includes first order absorption cooler 11, first order absorption storage tank 12
It is connected with the air inlet of first order absorption circulating pump 13, first order absorption cooler 11 with the synthesis tail gas supply source of alkyl dichloride phosphine
And the discharge port of first order absorption cooler 11 is connected with the feed inlet of first order absorption storage tank 12, the inlet of first order absorption storage tank 12
It is connected with soft water supply source and liquid outlet passes through first order absorption circulating pump 13 and primary cycle pipe 14 and first order absorption cooler 11
Inlet be connected, and first order absorption liquid outlet 15 is provided on primary cycle pipe 14.The conjunction of alkyl dichloride phosphine as a result,
Enter first order absorption after first order absorption cooler 11 is reacted with the soft water being pumped by first order absorption circulating pump at tail gas to store up
Tank 12, first order absorption liquid passes through again will after first order absorption circulating pump 13 is pumped into the interior circulation progress cyclic absorption of first order absorption cooler
Phosphorus containg substances absorb completely, and the tail gas not absorbed enters secondary cycle absorptive unit and carries out secondary cycle absorption.
Secondary cycle absorptive unit 20 includes second level tail gas absorber 21 and second level absorbent recirculation pump 22, second level tail gas absorption
The air inlet of tower 21 is connected with the gas outlet of primary cycle absorptive unit 10, the first inlet 25 of second level tail gas absorber with it is soft
Water supply source be connected and the liquid outlet of second level tail gas absorber lower part by second level absorbent recirculation pump 22 and secondary cycle pipe 23 with
Second inlet 26 on second level tail gas absorber top is connected, and second level absorbing liquid outlet is provided on secondary cycle pipe 23
24.The tail gas of the unit absorbed as a result, from primary cycle enters second level tail gas absorber 21 and carries out absorption processing, and second level absorbs
Liquid is pumped into second level tail gas absorber 21 again through second level absorbent recirculation pump 22 and carries out interior cyclic absorption, when in second level absorbing liquid
When hydrogen chloride mass concentration reaches 31~35%, then by second level absorbent recirculation pump 22 and second level absorbing liquid outlet 24 produce to
Hydrochloric acid by-product storage tank, the tail gas not absorbed enter three-level cyclic absorption unit.
Three-level cyclic absorption unit 30 includes three-level tail gas absorber 31 and three-level absorbent recirculation pump 32, three-level tail gas absorption
The air inlet of tower 32 is connected with the gas outlet of secondary cycle absorptive unit 20, the first inlet 35 of three-level tail gas absorber with it is soft
Water supply source be connected and the liquid outlet of three-level tail gas absorber lower part by three-level absorbent recirculation pump 32 and three-level circulation pipe 33 with
Second inlet 36 on three-level tail gas absorber top is connected, and three-level absorbing liquid outlet is provided on three-level circulation pipe 33
34.The tail gas of the unit absorbed as a result, from secondary cycle enters three-level tail gas absorber 31 and carries out absorption processing, and three-level absorbs
Liquid is pumped into three-level tail gas absorber 31 again through three-level absorbent recirculation pump 32 and carries out interior cyclic absorption, and the tail gas not absorbed is made
Atmosphere is sent into for exhaust gas or exhaust gas treatment unit is post-processed.
Preferably, the first inlet 25 of second level tail gas absorber also passes through recurrent canal 37 and three-level absorbing liquid outlet 34
It is connected, three-level absorbing liquid is returned into the absorbing liquid that absorbs as secondary cycle, while supplements into three-level tail gas absorber soft
Absorbing liquid of the water as three-level cyclic absorption.
Wherein, the circular flow of first order absorption circulating pump 13 is preferably 15~25m3/ h, when the stream of first order absorption circulating pump
It will appear entrained liquid phenomenon when measuring excessive, the phosphorous sour water of first order absorption liquid caused to be entrained to secondary cycle absorptive unit,
Make the reduction of hydrogen chloride by-product resource rate.The circular flow of second level absorbent recirculation pump 22 is preferably 10~20m3/ h, three-level absorb
The circular flow of circulating pump 32 is preferably 15~20m3/h.Internal circulating load is bigger more preferable for assimilation effect, but internal circulating load is excessive
To will lead to entrained liquid make previous stage absorbing liquid bring rear stage absorption tower by tail gas, therefore above-mentioned absorbent recirculation pump at different levels follows
Circulation is best setting range.
It should be understood that above embodiment and following embodiment that the present invention is described in detail are merely to illustrate the present invention rather than limit
The scope of the present invention processed, some nonessential improvement and tune that those skilled in the art's above content according to the present invention is made
It is whole to all belong to the scope of protection of the present invention.
The present invention is further explained in the light of specific embodiments.
The embodiment of the present invention is all made of method described above and equipment carries out the synthesis by-product chlorination of alkyl dichloride phosphine
The online purification process of hydrogen.
Embodiment 1 to 5:
After the total phosphorus content of first order absorption liquid in first order absorption storage tank reaches various concentration, using first order absorption liquid as containing
Phosphoric acid liquid is discharged and is transferred to waste acid treatment, and obtained Different Results are as shown in table 1 below.
The experimental result of 1 embodiment 1 to 5 of table
By the result of embodiment 1 to 5 it is found that the phosphorus containg substances of primary cycle absorptive unit remove when total phosphorus content is excessively high
Rate will decline, and lead to the reduction of hydrogen chloride resource rate, be optimal with 200~250g/L.
Embodiment 6 to 10:
The circular flow for controlling second level absorbent recirculation pump is 15m3The circular flow of/h and three-level absorbent recirculation pump is 15m3/
H, control first order absorption circulating pump are different circular flows, and continuous operating time is 10 days, then total phosphorus in first order absorption storage tank
Content is in 200g/L~250g/L, to removal rate such as the following table 2 of phosphorus containg substances.
The experimental result of 2 embodiment 6 to 10 of table
By the result of embodiment 6 to 10 it is found that if the circular flow of first order absorption circulating pump is excessive, it may appear that gas-liquid folder
Zoning causes the phosphorous sour water of first order absorption liquid to be entrained to secondary cycle absorptive unit, makes hydrogen chloride by-product resource rate
It reduces.
Embodiment 11 to 19:
The circular flow for controlling first order absorption circulating pump is 20m3/ h, control first order absorption storage tank in first order absorption liquid it is total
Phosphorus content controls second level absorbent recirculation pump and three-level absorbent recirculation pump is different circular flow in 200g/L~250g/L, with
On the basis of continuous operation 10 days, obtained Different Results are as shown in table 3 below.
The experimental result of 3 embodiment 11 to 19 of table
By the result of embodiment 11 to 19 it is found that the absorption that will lead to hydrogen chloride of internal circulating load deficiency is incomplete, and cause to provide
Source rate reduces；Biggish internal circulating load is equally able to achieve resource rate, but energy consumption will increase.Therefore most preferably second level absorption cycle
Pump circulation flow is 15m/h, and three-level absorbent recirculation pump circular flow is 15m/h.
In conclusion the method and apparatus that alkyl dichloride phosphine synthesis by-product hydrogen chloride of the present invention purifies online can be avoided
The consumption of liquid alkaline simultaneously reduces the cost of raw material, avoids the generation of phosphorous high-salt wastewater, and phosphorus containg substances removal rate reaches 99.9%,
Reduce the processing cost of the three wastes；The recycling for realizing by-product hydrogen chloride gas 98% simultaneously, has been made technical-grade hydrochloric acid pair
Product.
The invention is not limited to specific embodiments above-mentioned.The present invention, which expands to, any in the present specification to be disclosed
New feature or any new combination, and disclose any new processing method or process the step of or any new combination.
Claims (10)
1. a kind of method that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online, which is characterized in that by alkyl dichloride phosphine
Synthesis tail gas successively carry out the primary cycle using soft water as initial absorption solvent absorb, secondary cycle absorb and three-level circulation
It absorbs, absorbing liquids at different levels is periodically discharged and supplements lyosoption and exhaust gas is discharged after three-level cyclic absorption, wherein discharge
First order absorption liquid is phosphorous sour water, and the second level absorbing liquid of discharge is technical-grade hydrochloric acid.
2. the method that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to claim 1, which is characterized in that institute
Stating alkyl dichloride phosphine is dichloromethylphosphine or ethyl dichloride phosphine, and the phosphorus containg substances in the synthesis tail gas include tri-chlorination
Phosphorus and the alkyl dichloride phosphine.
3. the method that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to claim 1, which is characterized in that when
It is discharged when total phosphorus content reaches 100g/L~250g/L in the first order absorption liquid that the primary cycle absorbs as phosphorous sour water,
In, total phosphorus content is preferably 150g/L~250g/L in the first order absorption liquid, particularly preferably 200g/L~250g/L.
4. the method that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to claim 1, which is characterized in that when
It is discharged when HCl mass concentration is 31~35% in the second level absorbing liquid that the secondary cycle absorbs as technical-grade hydrochloric acid, wherein
HCl mass concentration is preferably 32~34% in second level absorbing liquid.
5. the method that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to claim 1, which is characterized in that will
The three-level absorbing liquid of three-level cyclic absorption discharge is supplemented to secondary cycle as the lyosoption that secondary cycle absorbs and absorbs, will be soft
Water is absorbed as primary cycle and the lyosoption of three-level cyclic absorption is supplemented to primary cycle and absorbs and three-level cyclic absorption.
6. a kind of equipment that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online, which is characterized in that the equipment includes string
Join primary cycle absorptive unit, secondary cycle absorptive unit and the three-level cyclic absorption unit of connection, the primary cycle absorbs
The air inlet of unit is connected with the synthesis tail gas supply source of alkyl dichloride phosphine, the gas outlet of primary cycle absorptive unit and second level
The air inlet of cyclic absorption unit is connected and the air inlet of the gas outlet of secondary cycle absorptive unit and three-level cyclic absorption unit
It is connected, the gas outlet of three-level cyclic absorption unit is connected with atmosphere or exhaust gas treatment unit.
7. the equipment that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to claim 6, which is characterized in that institute
Stating primary cycle absorptive unit includes first order absorption cooler, first order absorption storage tank and first order absorption circulating pump, and the level-one is inhaled
Receive cooler air inlet be connected with the synthesis tail gas supply source of alkyl dichloride phosphine and the discharge port of first order absorption cooler and
The feed inlet of first order absorption storage tank is connected, and the inlet of first order absorption storage tank is connected with soft water supply source and liquid outlet passes through level-one
Absorbent recirculation pump and primary cycle pipe are connected with the inlet of first order absorption cooler, are provided with level-one on the primary cycle pipe
Absorbing liquid outlet.
8. the equipment that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to claim 6, which is characterized in that institute
Stating secondary cycle absorptive unit includes second level tail gas absorber and second level absorbent recirculation pump, the air inlet of the second level tail gas absorber
Mouthful be connected with the gas outlet of primary cycle absorptive unit, the first inlet of second level tail gas absorber be connected with soft water supply source and
The liquid outlet of second level tail gas absorber lower part passes through second level absorbent recirculation pump and secondary cycle pipe and second level tail gas absorber top
The second inlet be connected, second level absorbing liquid outlet is provided on the secondary cycle pipe.
9. the equipment that the synthesis by-product hydrogen chloride of the alkyl dichloride phosphine according to any one of claim 6 to 8 purifies online,
It is characterized in that, the three-level cyclic absorption unit includes three-level tail gas absorber and three-level absorbent recirculation pump, the three-level tail gas
The air inlet on absorption tower is connected with the gas outlet of secondary cycle absorptive unit, the first inlet and soft water of three-level tail gas absorber
Supply source is connected and the liquid outlet of three-level tail gas absorber lower part passes through three-level absorbent recirculation pump and three-level circulation pipe and three-level tail
Second inlet on aspiration tower top is connected, and three-level absorbing liquid outlet is provided on the three-level circulation pipe.
10. the equipment that alkyl dichloride phosphine synthesis by-product hydrogen chloride purifies online according to claim 9, which is characterized in that
First inlet of the second level tail gas absorber also passes through recurrent canal and is connected with the three-level absorbing liquid outlet.
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| CN201910480703.1A CN110294458B (en) | 2019-06-04 | 2019-06-04 | Method and equipment for on-line purification of hydrogen chloride as byproduct in alkyl phosphine dichloride synthesis |
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