From the acetylene gas mixture, remove C
3+Above hydrocarbon impurities also reclaims the method for acetylene
Technical field
The present invention relates to the separation method of gas mixture, particularly adopt pressure and temperature varying absorption method separation of C from the acetylene unstripped gas
3 +The method of hydrocarbon impurities is closed in above insatiable hunger.
Background technology
The main source of acetylene is natural gas pyrolysis system acetylene and calcium carbide legal system acetylene, pollute because the technology of calcium carbide legal system acetylene can cause than serious environmental, so the development of this technology is restricted.At present the main source of acetylene is that natural gas pyrolysis generates acetylene, the thick acetylene that natural gas pyrolysis generates, through acetylene unit carry dense after purity about 98.4~99.0%, wherein major impurity is that hydrocarbon is closed in senior insatiable hunger: propadiene, methylacetylene, divinyl, vinylacetylene, diacetylene etc.In order to improve the purity of acetylene, make acetylene can be applicable to the chemical process that synthesizing vinyl acetate etc. is had relatively high expectations to purity acetylene, must the acetylene that natural gas pyrolysis makes be purified.
Removing at present senior insatiable hunger from the acetylene unstripped gas, to close the main method of hydrocarbon be vitriol oil absorption process.This method is to utilize the vitriol oil and senior insatiable hunger to close hydrocarbon 20 ℃~30 ℃ of temperature, and pressure is a little more than carrying out absorption reaction under the atmospheric condition.In the absorption reaction process, divinyl, vinylacetylene almost are removed entirely, and methylacetylene, propadiene are removed major part, and acetylene has small loss.The shortcoming of vitriol oil absorption process is that the vitriol oil has corrodibility, and the pipeline and the pump of its process corroded, and causes pipe leakage; Need in the absorption process to consume a large amount of vitriol oils, make running cost higher, and the discharging of useless vitriolic causes serious environmental to pollute.
Summary of the invention
Given this, the purpose of this invention is to provide and a kind ofly can make high purity acetylene and yield height, cost is low, non-environmental-pollution from the acetylene gas mixture, remove C
3 +Above hydrocarbon impurities also reclaims the method for acetylene.
The present invention adopts the pressure and temperature varying absorption method (PTSA) acticarbon is arranged and vacuumize step for twice to substitute vitriol oil absorption process and removes the middle-and-high-ranking insatiable hunger of acetylene and close hydrocarbon impurity and realize its purpose.
Of the present inventionly from the acetylene gas mixture, remove C
3 +Above hydrocarbon impurities also reclaims the method for acetylene, be in the pressure and temperature varying adsorption system of the circular flow of at least two adsorption beds that are filled with acticarbon, each adsorption bed of operation each time of system carries out adsorption step and regeneration step successively, wherein, the C of adsorption step in the charcoal absorption acetylene unstripped gas
3 +Above insatiable hunger is closed hydrocarbon impurities and is trapped in the adsorption bed, acquisition purifies acetylene gas discharge system and reclaims, the step that regeneration step experiences successively is: or the contrary I of putting, find time is arranged, add heat flush, isolation, cold blowing, the II that finds time, pressurising, the operational relation of each adsorption bed is preceding adsorption bed absorption back adsorption bed absorption beginning at the end, the pressure of above-mentioned adsorption step is 0.13~0.30MPa, and the resurgent gases of above-mentioned heating rinse step adopts and do not contain C
2 +The gas of above component and oxygen level<0.5%, its temperature are 70 ℃~200 ℃.
The specific surface area of above-mentioned gac is 500~1200m
2/ g.
Above-mentioned resurgent gases is at least a in the nitrogen, hydrogen, argon gas, carbon monoxide, carbonic acid gas, methane, ethane, ethene, acetylene of oxygen level<0.5%.
The gas that the above-mentioned I step of finding time is extracted out enters the pressure and temperature varying adsorption system again with after the acetylene raw material mixes.
In above-mentioned pressure and temperature varying absorption (PTSA) technology of the present invention, each adsorption bed is formed a continuous operation system, and details are as follows for the process that each adsorption bed is experienced in once circulating.
Adsorption step:
(1) absorption
Acetylene unstripped gas sending into from bottom to top had 0.13MPa~0.30MPa pressure, adsorb in the good adsorption bed of having regenerated, acticarbon is C to higher hydrocarbon in adsorption bed
3 +Above insatiable hunger is closed hydrocarbon impurities and is adsorbed, and the purification acetylene gas of acquisition is discharged from the adsorption bed top and reclaimed.When the forward position of adsorption zone is moved upwards up to the certain position of adsorption bed, the impurity propadiene reaches normality in purified gas after, can be considered this adsorption bed and reached state of saturation, end to send into the acetylene unstripped gas, stop absorption.
Regeneration step:
(2) against putting the promptly reverse pressure of putting
If the adsorption bed adsorptive pressure is higher than 0.15MPa, then put pressure suddenly, otherwise in next step the I that finds time by contrary strideing, too big and be easy to damage equipment to the surging force of evacuating equipment; If the adsorption bed adsorptive pressure is less than or equal to 0.15MPa, then do not need this step.
(3) I that finds time promptly once vacuumizes
Vacuumize with the adsorption bed of vacuum pump after, the gas in dead space in the adsorption bed and the absorbent particles is released, enter the pressure and temperature varying adsorption system again with after the acetylene raw material mixes, purify again, reduce the acetylene loss contrary putting, thus raising acetylene yield.
(4) add heat flush
With resurgent gases (nitrogen of oxygen level<0.5% or do not contain other gases that hydrocarbon is closed in senior insatiable hunger) through resurgent gases heater heats to 70 ℃~200 ℃, from top to bottom pass through adsorption bed, adsorption bed is washed, make the senior insatiable hunger that is adsorbed close the hydrocarbon desorb and discharge adsorption bed, acticarbon obtains regeneration.
(5) isolate
Close adsorption bed, wait for that other adsorption beds carry out corresponding steps.
(6) cold blowing
With the normal temperature resurgent gases adsorption bed that adds after the heat flush is washed, cools off, be cooled to normal temperature to adsorption bed.
(7) find time II, i.e. secondary vacuum pumping
Employing find time mode with vacuum pump with N in the adsorption bed
2Or other does not contain C
2 +The resurgent gases of above component is removed clean, to guarantee to purify purity of acetylene.
(8) pressurising
With purifying acetylene gas or acetylene unstripped gas adsorption bed is boosted to adsorptive pressure.
Each adsorption bed all experiences identical step, but staggers mutually on the sequential, and the operational relation of each adsorption bed is preceding adsorption bed absorption back adsorption bed absorption beginning at the end, carries out continuously to guarantee sepn process.
The present invention compares with existing vitriol oil absorption process, has following obvious advantage and unusual effect.
One, the present invention adopts pressure and temperature varying absorbing process (PTSA), hydrocarbon is closed in the senior insatiable hunger that separates and remove in the acetylene unstripped gas, the I step of finding time in the pressure and temperature varying absorbing process particularly, the pressure and temperature varying adsorption system is returned in the gas extraction that contains acetylene in the adsorption bed and in the sorbent material, purify again, to reduce the loss that purifies acetylene gas, improve the yield that purifies acetylene gas; The II step of finding time is thoroughly removed the regeneration off gases in the adsorption bed clean, purifies purity of acetylene to improve.Secondly, during according to the temperature of rising acticarbon, acticarbon closes the mechanism of the adsorptive capacity reduction of hydrocarbon impurity to senior insatiable hunger, adopt the heating rinse step in the present invention, with the resurgent gases after the heating acticarbon is heated, make the abundant desorb of acticarbon, thereby, abundant regeneration activity carbon adsorbent reduces its adsorptive power.Therefore, advantage of the present invention is the yield height of the purification acetylene gas that makes, and yield can reach 99.5%; Purification purity of acetylene height, purity can reach 99.4%.The present invention is that impurity such as 0.02%~0.80% propadiene, methylacetylene, divinyl, vinylacetylene can be removed to below the 400ppm the minimum 10ppm that reaches to content in the raw material acetylene gas; The decreasing ratio of methylacetylene>99.0%, propadiene decreasing ratio>96.0%.And the decreasing ratio of the methylacetylene of vitriol oil absorption process~95.0%, the decreasing ratio of propadiene~80.0%.
Two, the acticarbon of the present invention's employing has abundant central hole structure, and specific surface area is big, and it is C that hydrocarbon is closed in the senior insatiable hunger in the acetylene gas mixture
3 +The high adsorption capacity of hydrocarbon impurities is closed in above insatiable hunger, and is adding under the heat flush regeneration, and energy holomorphosis when therefore being used to purify the acetylene gas mixture, can obtain the acetylene purification gas of high purity, high yield.
Three, the cost of pressure and temperature varying adsorption method purification acetylene unstripped gas of the present invention is lower, for example the tolerance of acetylene unstripped gas is 4.5 tons/hour, 8000 hours production times calculated per year, adopt annual 7000 tons of the vitriol oils that consume of vitriol oil method, by 400 yuan of/ton calculating, only vitriol oil consumption just reaches 2,800,000 yuan/year.And adopt present method to handle the raw material acetylene gas of above-mentioned identical tolerance, and it installs raw-material consumption and only is 780,000 yuan/year, this shows that the consumption of this pressure and temperature varying absorption method is obviously low than vitriol oil absorption process, and its cost reduces significantly.
Four, during reproducing adsorbent of the present invention, if the resurgent gases that adopts is a nitrogen, then regeneration off gases can reach GB 16297-1996 discharging standards (the highest permission emission concentration of NMHC is 120mg/m
3), so regeneration off gases can high altitude discharge; As resurgent gases be oxygen level<0.5% do not contain C
2 +The inflammable gas of above component, then regeneration off gases can be burnt, and can not cause environmental pollution.
The inventive method is applicable to that natural gas pyrolysis system acetylene or other contain the deep purifying processing that the acetylene gas of hydrocarbon is closed in senior insatiable hunger.
Below, with embodiment and accompanying drawing thereof the present invention is further described again.
Description of drawings
Fig. 1 of the present inventionly a kind ofly removes C from the acetylene gas mixture
3 +Above hydrocarbon impurities also reclaims the process flow diagram of the method for acetylene.Show three tower PTSA acetylene purification flow processs.
Fig. 2 is that another kind of the present invention removes C from the acetylene gas mixture
3 +Above hydrocarbon impurities also reclaims the process flow diagram of the method for acetylene.Show three tower PTSA acetylene purification flow processs.
Embodiment
Embodiment 1
Of the present inventionly a kind ofly from the acetylene gas mixture, remove C
3 +Above hydrocarbon impurities also reclaims the method for acetylene, and technical process as shown in Figure 1.
Pressure and temperature varying adsorption system of the present invention is a kind of pressure and temperature varying adsorption unit of three bed structures, by adsorption bed A tower, B tower, the C tower of three tower structures, vacuum pump, resurgent gases well heater, connecting pipeline, formations such as by-pass valve control.The sorbent material that loads in three adsorption beds is that to have the specific surface area that abundant central hole structure and appropriate bore distribute be 500~1200m
2/ g gac.The working procedure of each adsorption bed and three operational relations that adsorption bed is mutual, promptly the processing step sequential of three adsorption beds sees Table 1.Technology with the A tower is row explanation the inventive method below.
When system moves, press each by-pass valve control of programming Control, pressure 0.15MPa, flow 3877 Nm by computer
3The acetylene unstripped gas of/h is sent into the A tower through gas-liquid separator, pipeline 10, valve 1A, the A tower enters adsorption step, last 240 minutes, senior insatiable hunger in the gas is closed hydrocarbon by the charcoal absorption in the tower and be detained in the tower, and the acetylene purification gas that is not adsorbed enters acetylene product conduit 20 and reclaims through valve 2A.Have only valve 1A, valve 2A to open with the valve that the A tower links this moment, and all the other valves then are in closing condition.After A tower absorption was finished, sorbent material had been inhaled senior insatiable hunger saturated and has been closed hydrocarbon in the A tower, and shut-off valve 1A, valve 2A regenerate to the sorbent material in the A tower.
The A tower enters regeneration step, and open valve 4A, valve 2 and vacuum pump last 10 minutes through 30 pairs of A towers of pipeline I that finds time, and the gas (mainly being acetylene) extracted out in the tower is returned the pipeline 10 of acetylene unstripped gas, shut-off valve 4A, valve 2 and vacuum pump through pipeline 40; Follow open valve 5A, valve 3A, resurgent gases through the resurgent gases well heater with the steam-heated cal(l)andria to 70 that feeds ℃~200 ℃, enter the A tower through pipeline 50, valve 5A, add heat flush, last 210 minutes, to add heat-adsorbent, along with whole sorbent material constantly is heated, the senior insatiable hunger that is adsorbed in the sorbent material is closed hydrocarbon also constantly by desorb, stripping gas is that regeneration off gases is discharged the A tower from valve 3A, to the regeneration off gases water cooler, cooled stripping gas is sent through separator, waste line, or burning or high altitude discharge through pipeline 60.Close whole turnover valves of A tower subsequently, isolated 30 minutes; Open valve 6A, valve 4A send the resurgent gases of normal temperature into the A tower then, by whole adsorption bed, carry out cold blowing, last 210 minutes, the heat that accumulates in the A tower is taken away, be cooled to envrionment temperature, close 6A then, cold blowing gas is discharged behind the adsorption bed resurgent gases as the C tower; Then open valve 2 and vacuum pump through 30 pairs of A towers of pipeline II that finds time, last 10 minutes, extract shut-off valve 2 and valve 4A behind the cold blowing gas residual in the A tower out; Open valve 7A will purify acetylene gas and send into the A tower, carry out pressurising to the A tower, last 10 minutes, pressurising till its pressure reaches adsorptive pressure, shut-off valve 7A immediately.The A tower is finished a technological cycle.
B tower in the native system, C tower are identical with the step of A tower experience, just stagger mutually on the sequential.As shown in table 1, when the A tower adsorbs the beginning of B tower absorption at the end,, B tower bed begins when adsorbing C tower absorption at the end, and the A tower begins absorption once more when the C tower adsorbs at the end, and the rest may be inferred, and circulation is carried out, and system is carried out continuously.
The yield of the purification acetylene gas that present embodiment makes can reach 99.5%, and purity can reach 99.4%, contains propadiene≤400ppm, methylacetylene<100ppm, 1,3-butadiene<100ppm, vinylacetylene<100ppm.
Present embodiment is specially adapted to natural gas pyrolysis system acetylene or other contain the deep purifying processing that the acetylene gas of hydrocarbon is closed in senior insatiable hunger.
Embodiment 2
Of the present inventionly a kind ofly from the acetylene gas mixture, remove C
3 +Above hydrocarbon impurities also reclaims the method for acetylene, and technical process as shown in Figure 2.
The pressure and temperature varying adsorption system of present embodiment and operation are substantially the same manner as Example 1, it also is a kind of pressure and temperature varying adsorption unit of three bed structures, the sorbent material that loads in the adsorption bed is identical with embodiment 1, the working procedure of each adsorption bed and three operational relations that adsorption bed is mutual, promptly the processing step sequential of three adsorption beds sees Table 2.Therefore present embodiment is characterized in having contrary strideing suddenly because adsorptive pressure is higher than 0.15MPa in regeneration step.
During the operation of system, pressure is 0.25MPa, flow 4000Nm
3The acetylene unstripped gas of/h enters the A tower through gas-liquid separator, pipeline 10, valve 1A, carries out adsorption step, lasts 240 minutes, obtains acetylene purification gas and enters acetylene product conduit 20 through valve 2A.After the absorption of A tower was finished, shut-off valve 1A, valve 2A regenerated to the sorbent material in the A tower.
The A tower enters regeneration step, and the A tower at first carries out contrary putting 5 minutes, i.e. open valve 4A is put to normal pressure the A pressure tower is contrary through pipeline 30 and 70, and the pipeline 10 of acetylene unstripped gas is returned in contrary venting after the supercharger supercharging; Open valve 2 and vacuum pump last 5 minutes through 30 pairs of A towers of pipeline I that finds time again subsequently, and the gas of extraction returns the pipeline 10 of acetylene unstripped gas, shut-off valve 4A, valve 2 and vacuum pump through pipeline 40; Follow open valve 5A, valve 3A, resurgent gases through the resurgent gases well heater with the steam-heated cal(l)andria to 70 that feeds ℃~200 ℃, enter the A tower through pipeline 50, valve 5A, add heat flush, last 210 minutes, stripping gas is discharged the A tower from valve 3A, arrives the regeneration off gases water cooler through pipeline 60, cooled stripping gas is sent through separator, waste line, or burning or high altitude discharge.Close whole turnover valves of A tower subsequently, isolated 30 minutes; Open valve 6A, valve 4A send the resurgent gases of normal temperature into the A tower then, carry out cold blowing, last 210 minutes, close 6A after being cooled to envrionment temperature, and cold blowing gas is discharged behind the adsorption bed resurgent gases as the C tower; Then open valve 2 and vacuum pump through 30 pairs of A towers of pipeline II that finds time, last 10 minutes, shut-off valve 2 and valve 4A; Open valve 7A will purify acetylene gas and send into the A tower, carry out pressurising to the A tower, last 10 minutes, till pressure reaches adsorptive pressure, and shut-off valve 7A immediately.The A tower is finished a technological cycle.
B tower in the native system, C tower are identical with the step of A tower experience, just stagger mutually on the sequential, and the step of each adsorption bed and mutual operational relation are as shown in table 2, and be identical with embodiment 1.
The yield of the purification acetylene gas that present embodiment makes can reach 99.5%, and purity can reach 99.4%, contains propadiene≤400ppm, methylacetylene<100ppm, 1,3-butadiene<100ppm, vinylacetylene<100ppm.
Present embodiment is specially adapted to natural gas pyrolysis system acetylene or other contain the deep purifying processing that the acetylene gas of hydrocarbon is closed in senior insatiable hunger.
The processing step time-scale of table one:
embodiment 1
The A tower | ????????????????A | ????V
1 | ????H | ????????????IS | ????C | V
2 | R |
The B tower | ??IS | ????C | V
2 | R | ??????????????A | ????V
1 | ????H | ????IS |
The C tower | ??V
1 | ????H | ????????IS | ????C | ??V
2 | ??R | ??????????????A |
The processing step time-scale of table two:
embodiment 2
The A tower | ??????????????A | ?D | ?V
1 | ????H | ????????????IS | ????C | V
2 | R |
The B tower | ??IS | ????C | ???V
2 | R | ????????????????A | ?D | V
1 | ????H | ????IS |
The C tower | D | V
1 | ????H | ????????????IS | ????C | ??V
2 | ??R | ????????????????A |
In the table: the contrary V of putting of A-absorption D-
1-I the H-that finds time adds heat flush
IS-isolates C-cold blowing V
2-II R-the pressurising of finding time