CN106943864A - A kind of method that carbon material selective absorbing purifies acetylene - Google Patents

A kind of method that carbon material selective absorbing purifies acetylene Download PDF

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Publication number
CN106943864A
CN106943864A CN201610411057.XA CN201610411057A CN106943864A CN 106943864 A CN106943864 A CN 106943864A CN 201610411057 A CN201610411057 A CN 201610411057A CN 106943864 A CN106943864 A CN 106943864A
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China
Prior art keywords
acetylene
carbon material
purifies
selective absorbing
ionic liquid
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CN201610411057.XA
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Chinese (zh)
Inventor
刘伟海
杜君
施彦斌
高尚
肖祥
余江
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Beijing University of Chemical Technology
Xinjiang Zhongtai Chemical Co Ltd
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Beijing University of Chemical Technology
Xinjiang Zhongtai Chemical Co Ltd
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Priority to CN201610411057.XA priority Critical patent/CN106943864A/en
Publication of CN106943864A publication Critical patent/CN106943864A/en
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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
    • B01D53/02—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 adsorption, e.g. preparative gas chromatography
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/38—Removing components of undefined structure
    • 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
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/81—Solid phase processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/22—Aliphatic unsaturated hydrocarbons containing carbon-to-carbon triple bonds
    • C07C11/24—Acetylene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/12—Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/102—Carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/55—Compounds of silicon, phosphorus, germanium or arsenic

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biomedical Technology (AREA)
  • Water Supply & Treatment (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

Produced the invention discloses one kind using carbon material selective absorbing calcium carbide in acetylene gas technique and produce PH3Deng the method for impurity.Acetylene gas is handled by using the selective absorption of the carbon material such as activated carbon, activated carbon fiber, as a result shows carbon material to the PH in acetylene3Not only there is good selective absorbing effect etc. foreign gas, and regeneration Posterior circle can be carried out using hot-air or Metal Substrate ionic liquid and use.Dangerous pollutant PH in acetylene gas technique is produced to calcium carbide3Reach that selectivity efficient absorbs the purpose with recycling, with certain economic benefit and social benefit.

Description

A kind of method that carbon material selective absorbing purifies acetylene
Technical field
The present invention relates to the PH produced in a kind of utilization carbon material selective absorption processing calcium carbide method acetylene production gas technique3 It is a kind of industrial process gas purification process technique Deng the method for impurity.
Background technology
Acetylene (C2H2) it is usually used in the cutting, welding and metal surface spraying plating of metal, also as the important original of petrochemical industry Material, for manufacturing polyvinyl chloride, neoprene, acetic acid and vinylacetate etc..The industrial method for producing acetylene is a lot, such as electricity Shi Fa, methane cracking method, hydrocarbon cracking method etc..China mainly uses carbide at present, the normal quilt of the acetylene gas produced with carbide It is called acetylene.
The main component of calcium carbide is CaC2, but wherein often contain a small amount of or micro CaS, Ca3P2Deng impurity.When calcium carbide with Water react production acetylene while, produce accessory substance H2S and PH3Deng.Especially with PH in these accessory substances3It is most dangerous, it is first First, if containing the PH up to 200ppm or higher amount in acetylene gas3When, it can significantly reduce its self-ignition point, can be sent out at 100 DEG C Combustion is born from, there is serious disaster hidden-trouble；Secondly, PH3For hypertoxic gas, producers are produced using impure acetylene During, easily suck PH therein3Gas, serious threat is produced to healthy；Again, also PH3Acetylene gas exist During carrying out weld job, welding position is produced brittle phenomenon, have crack appearance after metal cooling when serious, have A little then occur inside welding position compared with crackle, this is for the mining equiment of overhaul, and it is dangerous bigger.
PH in acetylene3、H2S、AsH3There is stronger reduction reaction ability Deng impurity, so industrial frequently with oxygen Change reducing agent and these impurity carry out redox reaction, reach the purpose of purification.Dry method is divided into according to the state of cleanser net Change and two kinds of wet cleaning.
Usually used cleanser has ferric trichloride, bleaching powder, bichromate etc. in dry cleaning.Dry purification process Because its construction investment is few, equipment is simple, and the features such as detergent power is larger is generally selected by many enterprises, but dry purification process Also have the disadvantage that：
(1) hydrochloric acid and hydrogen severe corrosion equipment are produced in purification.
(2) due to containing phosphorus in cleanser, so being rubbed when changing cleanser with instrument, it is likely that cause fire Calamity.
(3) purification is costly, and the purification expense of every bottle of acetylene gas adds the production of acetylene gas at 0.5~1.0 yuan or so Cost.
(4) because of (HgC1 of mercury chloride containing co-catalyst2), stannous chloride (CuC1), so must when cleanser is scrapped in processing Secondary pollution problem must be considered；I.e. substantial amounts of discarded cleanser needs to make burial processing.
Wet processing is mainly absorbed with sodium hypochlorite, and device processing is simple, and small investment is corrosion-resistant, but equally exists The available chlorine content of some problems, such as sodium hypochlorite is difficult to control to, the control of pH value of solution, and temperature and pressure is controlled in purification technique The problems such as, increase the difficulty of operation.
Carbon material is the good adsorbent of a class, and its specific surface area is big, and surface and internal gutter are intensive, adsorption rate it is fast and Favorable regeneration effect, in recent years as the adsorbent or the adsorbing agent carrier quilt of chemisorbed of a kind of selectivity efficient physical absorption It is widely studied.If by the PH in acetylene3Efficient absorption purification is carried out with carbon material, the purity of acetylene gas is on the one hand added, The potential safety hazard during acetylene use is relieved, is on the other hand PH3Recycling create premise.
The content of the invention
Given birth to it is an object of the invention to provide a kind of by the selective absorbing effect effectively purification of carbon material with carbide The PH produced in production acetylene technical process3Deng impurity, the purity of acetylene is improved, it is to avoid being present in for bringing due to impurity presence PH in potential safety hazard during use, more impurity3Recycling Deng material creates premise.
The present invention is with the PH in acetylene3For main remover matter, by using cocoanut active charcoal, coal mass active carbon, This several carbon material of polyacrylonitrile radical active carbon fiber, viscose-based active carbon fiber are to the PH in simulation acetylene3Impurity is carried out Remove, observe it to PH3Static state and Dynamic Adsorption, probe into different condition by adjusting the conditions such as reaction temperature, pressure, steam Under to PH in acetylene gas3The removal efficiency of foreign gas, and it is regenerative agent spy to be utilized respectively hot-air and Metal Substrate ionic liquid The desorption and regeneration performance of carbon material is studied carefully.As a result show carbon material to the PH in acetylene3Have good selective absorbing Effect, and carbon material regenerated in the presence of hot-air or Metal Substrate ionic liquid, wherein regenerated with hot air is empty using heat Gas is to absorption PH3Carbon material carry out purging and be desorbed it, and the regeneration of Metal Substrate ionic liquid will using Metal Substrate ionic liquid The PH of carbon material absorption3It is oxidized to H3PO4And remove, the Metal Substrate ionic liquid after regeneration can be regenerated itself with air. Thus reaction system can repeat absorption dephosphorization-desorption and regeneration or adsorb dephosphorization-oxidation regeneration.Acetylene gas is produced to calcium carbide Dangerous pollutant PH in technique3Selectivity efficient absorption, and PH are reached3The recycling of gas is laid a good foundation.
The present invention solves above-mentioned technical problem with following technical scheme：
The process step of the invention is：
(1) carbon material is filled in adsorption reaction device；
(2) acetylene is passed through progress adsorption cleaning reaction in adsorption reaction device；
(3) gas after adsorption cleaning is monitored after adsorbent equipment discharge with analytical and testing instrument；
(4) carbon material after adsorbing contaminant is regenerated；
(5) carbon material after regenerating is again filled with as recycled after adsorption reaction device.
Further, carbon material of the present invention includes cocoanut active charcoal, coal mass active carbon, polyacrylonitrile radical active carbon The carbon materials such as fiber, viscose base activated carbon fiber.
Further, acetylene of the present invention contains PH for what is produced in calcium carbide production acetylene gas technique3Deng impurity Impure acetylene gas.
Further, in step of the present invention (2), adsorption reaction condition is normal temperature and pressure.
Further, in step of the present invention (4), the method for regenerating carbon material can be warm air blowoff regeneration Method, or ionic liquid oxidation reclaiming process.
Further, regeneration hot air temperature of the present invention is at 40~80 DEG C.
Further, regeneration of ionic liquid of the present invention is with certain by iron-based ionic liquid and palladium base ionic liquid The compound ion liquid that volume ratio is mixed into.
Further, ionic liquid of the present invention can be carried out again after being regenerated to carbon fiber with air to it It is raw.
Further, iron-based ionic liquid of the present invention by chlorinated butyl methylimidazole with ferric chloride (FeCl36H2O) to rub You compare 1:It is 2-in-1 into described palladium base ionic liquid is by chlorinated butyl methylimidazole and palladium bichloride with mass ratio 49:1 synthesis.
It is in place of the characteristic of the present invention：
(1) technique is simple, and security is good：Using carbon material directly to PH3Selective absorbing is carried out, without addition catalysis Agent, i.e., need not consider that acetylene gas occurs chemical change and gone bad, without consideration PH3Generation chemical change etching apparatus and generation The problems such as spontaneous combustion, be PH3Recycling create premise.
(2) it is with low cost, good absorbing effect：Carbon material is efficient with the avtive spot in its huge specific surface area and duct Absorb PH3, cost is reduced, good removal effect can be obtained again.
(3) regenerability is good：Carbon material is due to being to adsorb dephosphorization, and regenerability is good, to PH3Repeat after absorption-regeneration Still keep good assimilation effect.
(4) can harmless treatment：The PH of carbon material absorption3Deng impurity, carried out using Metal Substrate ionic liquid further Processing, makes PH while carbon material is regenerated3It is oxidized to H3PO4, reach the harmless treatment to acetylene.
Brief description of the drawings
Fig. 1 is PH in selective absorbing of the present invention removing acetylene3The technological process of impurity；
Fig. 2 is dephosphorization performance curve of the Viscose-based ACF in continuous adsorption-regeneration process；
Fig. 3 is PH in cocoanut active charcoal absorption acetylene3Flow-time of break-through curve；
Fig. 4 is PH in absorption acetylene after warm air blowoff regeneration cocoanut active charcoal3Recovery time-time of break-through it is bent Line；
Fig. 5 is PH in absorption acetylene after Metal Substrate ionic liquid oxidation regeneration cocoanut active charcoal3Recovery time-penetrate Time graph.
Embodiment
Below by embodiment, and it is equipped with accompanying drawing technical scheme is further described, but the present invention is not It is limited to following embodiments.
Embodiment 1：
The viscose-based active carbon fiber for taking 6.67g fresh is loaded into the adsorbent equipment such as Fig. 1, PH3Concentration is 1000ppm, flow is passed through reactor for 30mL/min simulation acetylene and carries out Dynamic Adsorption at normal temperatures and pressures, every 10min detections absorb after phosphorus content in tail gas, to reach and be blown into reaction with 40~80 DEG C of hot-air again after adsorption saturation Device carries out purging regeneration, and adsorption-regeneration three times repeatedly can still keep good assimilation effect, adsorption curve is as shown in Figure 2.
Embodiment 2：
The polyacrylonitrile radical active carbon fiber for taking 10g fresh is placed in adsorbent equipment as shown in Figure 1, after device is vacuumized At room temperature to PH3Carry out static absorption experiment, initial pressure 0.05MPa.The pressure of static adsorption equilibria can reach 0.02MPa, adsorbance is up to 21mg PH3/g.Show carbon material to PH3Static Adsorption effect it is fine.
Embodiment 3：
The cocoanut active charcoal for taking 96g fresh is placed in adsorbent equipment as shown in Figure 1, is passed through acetylene, PH3Concentration is 1000ppm, it is respectively 30mL/min, 40mL/min, 50mL/min, 60mL/min that acetylene, which is passed through flow, records optimal purification Time, (adsorbent equipment was worked off one's feeling vent one's spleen middle PH3Concentration is approximately more than 10ppm time), make flow-time of break-through curve as shown in Figure 3 Figure.
Embodiment 4：
It is coconut activated after adsorbing contaminant when the present embodiment is that acetylene is passed through flow for 50mL/min in Example 3 After charcoal, warm air blowoff 30min, 60min, 90min, 120min through 40L/h, it is again loaded into adsorption reaction device, calcium carbide Throughput is 50mL/min, records the optimal clarification time, makees recovery time-time of break-through curve map as shown in Figure 4.
Embodiment 5：
The present embodiment is acetylene in Example 3, is passed through flow for 30mL/min, coconut activated after adsorbing contaminant In charcoal, the regenerating unit for entering Fig. 1, with peristaltic pump with certain flow respectively by the circulation of 100mL Metal Substrates ionic liquid to work Property charcoal regeneration 30min, 60min, 120min, ionic liquid needs to enter by 60mL/min air before being recycled into regenerating unit Row regeneration.It is fed again into after the scrubbed drying of activated carbon after regeneration in adsorbent equipment, calcium carbide throughput is 30mL/min, note The optimal clarification time is recorded, makees recovery time-time of break-through curve map as shown in Figure 5.
By embodiment 3,4,5 as can be seen that activated carbon is physical adsorption process, thing to the purification absorption process of acetylene gas Manage the adsorption process rate of adsorption very fast.When hot-air is by activated carbon after the completion of absorption, it can be formed on the surface of activated carbon Impurity gas in negative pressure, activated carbon can be parsed, so as to reach the purpose of absorption-parsing regeneration.Metal Substrate ionic liquid Body regeneration is related to redox chemical reaction process, by the oxidation of impurities being adsorbed in activated carbon into H3PO4Deng material, simultaneously Renewal is continuously available self by air regenesis, the process of the adsorbing-oxidising regeneration different from warm air blowoff is formd, to work The regeneration effect of property charcoal is significantly improved.

Claims (9)

1. a kind of method that carbon material selective absorbing purifies acetylene, it is characterised in that mainly comprise the following steps：
(1) carbon material is filled in adsorption reaction device；
(2) acetylene is passed through progress adsorption cleaning reaction in adsorption reaction device；
(3) gas after adsorption cleaning is monitored after adsorbent equipment discharge with analytical and testing instrument；
(4) carbon material after adsorbing contaminant is regenerated；
(5) carbon material after regenerating is again filled with as recycled after adsorption reaction device.
2. the method that a kind of carbon material selective absorbing according to claim 1 purifies acetylene, it is characterised in that described Carbon material include the carbon materials such as cocoanut active charcoal, coal mass active carbon, polyacrylonitrile radical active carbon fiber, viscose base activated carbon fiber Material.
3. the method that a kind of carbon material selective absorbing according to claim 1 purifies acetylene, it is characterised in that described Acetylene be carbide produce the impure acetylene gas containing impurity such as PH3.
4. the method that a kind of carbon material selective absorbing according to claim 1 purifies acetylene, it is characterised in that described The step of (2) in, adsorption reaction condition be normal temperature and pressure.
5. the method that a kind of carbon material selective absorbing according to claim 1 purifies acetylene, it is characterised in that described The step of (4) in, regeneration carbon material method can be warm air blowoff method of reproduction, or ionic liquid oxidation regeneration Method.
6. the method that a kind of carbon material selective absorbing according to claim 5 purifies acetylene, it is characterised in that described Regeneration hot air temperature at 40~80 DEG C.
7. the method that a kind of carbon material selective absorbing according to claim 5 purifies acetylene, it is characterised in that described Regeneration of ionic liquid be the compound ion liquid being mixed into by iron-based ionic liquid and palladium base ionic liquid with certain volume ratio.
8. the method that a kind of carbon material selective absorbing according to claim 5 purifies acetylene, it is characterised in that described Ionic liquid it can be regenerated with air after being regenerated to carbon fiber.
9. the method that a kind of carbon material selective absorbing according to claim 7 purifies acetylene, it is characterised in that described Iron-based ionic liquid by chlorinated butyl methylimidazole and ferric chloride (FeCl36H2O) with mol ratio 1:It is 2-in-1 into described palladium base ion Liquid is by chlorinated butyl methylimidazole and palladium bichloride with mass ratio 49:1 synthesis.
CN201610411057.XA 2016-06-13 2016-06-13 A kind of method that carbon material selective absorbing purifies acetylene Pending CN106943864A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109107551A (en) * 2018-09-18 2019-01-01 浙江蓝德能源科技发展有限公司 A kind of device and method using ionic liquid regenerated carbon
CN109621634A (en) * 2019-01-18 2019-04-16 四川天科技股份有限公司 A kind of method and device system of carbide acetylene purification

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109107551A (en) * 2018-09-18 2019-01-01 浙江蓝德能源科技发展有限公司 A kind of device and method using ionic liquid regenerated carbon
CN109621634A (en) * 2019-01-18 2019-04-16 四川天科技股份有限公司 A kind of method and device system of carbide acetylene purification
CN109621634B (en) * 2019-01-18 2023-08-25 西南化工研究设计院有限公司 Method, device and system for purifying acetylene by calcium carbide

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Application publication date: 20170714