CN112250540B - Method for separating R134a, R133a and R124 from rectification heavy component - Google Patents
Method for separating R134a, R133a and R124 from rectification heavy component Download PDFInfo
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- CN112250540B CN112250540B CN202011097120.XA CN202011097120A CN112250540B CN 112250540 B CN112250540 B CN 112250540B CN 202011097120 A CN202011097120 A CN 202011097120A CN 112250540 B CN112250540 B CN 112250540B
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000011084 recovery Methods 0.000 claims abstract description 224
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 238000010992 reflux Methods 0.000 claims abstract description 29
- 238000003825 pressing Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 230000001105 regulatory effect Effects 0.000 claims description 78
- 238000000605 extraction Methods 0.000 claims description 24
- 239000003507 refrigerant Substances 0.000 claims description 21
- 239000012043 crude product Substances 0.000 claims description 19
- 238000007599 discharging Methods 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000005070 sampling Methods 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- JQZFYIGAYWLRCC-UHFFFAOYSA-N 1-chloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)C(F)(F)Cl JQZFYIGAYWLRCC-UHFFFAOYSA-N 0.000 description 1
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000344 non-irritating Toxicity 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/38—Separation; Purification; Stabilisation; Use of additives
- C07C17/383—Separation; Purification; Stabilisation; Use of additives by distillation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for separating R134a, R133a and R124 from a rectification heavy component, which comprises the following operation steps: firstly, pressing heavy components in a residual liquid tank of a rectifying tower to a buffer tank, and then feeding the heavy components into a recovery tower from the buffer tank; then, heating and boosting the recovery tower, maintaining the pressure of the recovery tower at 0.6MPa, and performing total reflux operation; r134a is extracted after 20-30min of reflux, and R124 is emptied when the temperature of the top of the recovery tower reaches 35 ℃; when the temperature of the top of the recovery tower is higher than 55 ℃, R133a is extracted; according to the invention, the original separation process is improved, and R124 is selectively vented at the reflux temperature of 35 ℃, so that the recovery rate of R124 is improved, and meanwhile, the amounts of R133a and R134a doped in R124 are obviously reduced, so that the waste of R133a and R134a is reduced, and the recovery rates of R133a and R134a are improved.
Description
Technical Field
The invention relates to the technical field of chemical separation and purification, in particular to a method for separating R134a, R133a and R124 from rectified heavy components.
Background
R134a (Chinese name: 1, 2-tetrafluoroethane), which is a refrigerant having no chlorine atom, no damage to the ozone layer, and good safety (nonflammable, non-explosive, nontoxic, non-irritating, non-corrosive), has refrigerating capacity and efficiency very close to those of R-12 (dichlorodifluoromethane, freon), and is thus considered as an excellent long-term substitute refrigerant.
There are tens of methods reported for synthesizing R134a, but only two methods are adopted in actual industrial production: trichloroethylene (TCE) route and tetrachloroethylene (PCE) route.
The R134a production process adopted by the company is a Trichloroethylene (TCE) route method, namely, trichloroethylene (TCE) and Hydrogen Fluoride (HF) are used as raw materials, under the action of a catalyst, the first step of addition and substitution reaction is carried out to generate 1, 1-trifluoro-2-chloroethane (R133 a), and then the R134a is further fluorinated at a higher temperature.
The raw materials generate R133a, R124, R134a, R143a, HCL, HF (raw material residue) and the like in a reaction system, wherein the HCL is absorbed by a HCL separating tower to prepare hydrochloric acid, so that a small amount of residual HCL and HF (raw material residue) are removed from reaction products, and the hydrochloric acid is removed by water washing and alkali washing procedures. In this case, the components in the reaction product are mainly R134a (product), R133a (intermediate yield, and HF-producing product R134 a), R124 (heavy impurity component), and R143a (light impurity component), and the light component R143a can be removed by the separation of the degasser. Because the boiling point of R133A, R124 is higher than that of R134a, R134a is produced from the top of the rectifying tower to a subsequent product filling system, and R133A, R124 and the like are enriched in the rectifying tower kettle, and by periodically discharging into a rectifying tower residual liquid tank, substances such as R133A, R124, R134a (with density higher than water) and a small amount of water in the rectifying tower residual liquid tank are subjected to standing delamination according to density, moisture in the rectifying tower residual liquid tank is periodically discharged, and the residual substances such as R133A, R124 and R134a are sent to a buffer tank (V-123A), and a recovery tower operation is performed to separate the R133A, R124 and R134a from the mixed components.
Wherein R133a (Chinese name: 1, 1-trifluoro-2-chloroethane), which is an important intermediate for pesticides, medicines and freon substitutes, can prepare CFCl13a and HCFCL23 by photochlorination or thermochlorination from Rl33 a; a series of products such as Rl34a and the like can be prepared by deep-temperature fluorination.
R124 (Chinese name: tetrafluoro-chloroethane), R124 is mainly used as the refrigerant of high temperature air conditioner, and is also the important component of the mixed working medium, and R409A/R401A is mixed. R124 can also be used as a fire extinguishing agent, and can replace freon CFC-114.
At present, when R133a, R124 and R134a in a recovery tower are separated, the recovery rate of the R124 separated by the adopted process is low, and a large amount of R133a and R134a are doped in the recovery tower, so that the recovery rate of the R133a and the R134a is low, and the resource waste is serious.
Therefore, there is a need to provide a new solution to overcome the above-mentioned drawbacks.
Disclosure of Invention
The invention aims to provide a method for separating R134a, R133a and R124 from rectified heavy components, which can effectively solve the technical problems.
In order to achieve the purpose of the invention, the following technical scheme is adopted:
a process for separating R134a, R133a and R124 from a rectified heavy fraction comprising the following operative steps:
step 1: pressing heavy components in a residual liquid tank of the rectifying tower to a buffer tank, and feeding the heavy components into a recovery tower from the buffer tank;
step 2: heating and boosting the recovery tower, maintaining the pressure of the recovery tower at 0.5-0.7MPa, and performing total reflux operation;
step 3: after 20-30min of reflux, opening a channel from the top of the recovery tower to the R134a crude product tank, and opening a recovery tower top extraction regulating valve to extract R134a to R134a crude product tanks from the R134a to the R134a crude product tank;
step 4: when the temperature of the top of the recovery tower reaches 30-40 ℃, and the temperature of the bottom of the recovery tower reaches 55-60 ℃, opening a top emptying valve to empty R124;
step 5: when the temperature of the top of the recovery tower is higher than 55 ℃, opening a channel from the recovery tower to the recovery tank, and opening a recovery tower top extraction regulating valve to extract R133a to the recovery tank;
step 6: when the liquid level in the recovery tower is reduced to 380-420mm, stopping the operation of the recovery tower, and pressing the material in the bottom of the recovery tower to a residual liquid tank of the recovery tower;
step 7: repeating the steps, and pressing the materials in the recovery tank into the accident tank when the liquid level in the recovery tank reaches 170-190 cm.
Preferably, in the whole reflux operation in the step 2, the pressure of the recovery tower is 0.6MPa.
Preferably, the temperature at the top of the recovery tower is 35 ℃ when the R124 is discharged in the step 4.
Preferably, when the recovery tower stops operating in the step 6, the liquid level in the recovery tower is 400mm.
Preferably, in the step 7, when the liquid level in the recovery tank reaches 180cm, the material in the recovery tank is pressed into the accident tank.
Preferably, the operation flow of the step 1 specifically includes:
a) When the temperature of the rectifying tower kettle is higher than 75 ℃, an inner operator opens a discharging regulating valve of the rectifying tower kettle to divide the recombinant pressure in the rectifying tower residual liquid tank to a buffer tank;
b) When the liquid level of the buffer tank is more than 1000mm, an inner operator informs an outer operator to open an inlet valve and an outlet valve of a refrigerant regulating valve of a condenser at the top of the recovery tower, a refrigerant outlet valve, front and rear valves of a steam regulating valve of the recovery tower kettle and a condensed water outlet valve of a shell side of the recovery tower kettle;
d) Then an outer operator opens a front valve of a recovery tower top extraction regulating valve and a regulating valve discharging valve, and an inner operator opens the recovery tower top extraction regulating valve to discharge the pressure of the recovery tower to 0;
e) Finally, an external operator opens a discharge valve at the bottom of the buffer tank and a feeding valve at the bottom of the recovery tower, and feeds the recovery tower by using the pressure difference, and when the liquid level of the recovery tower reaches 1600mm, the feeding to the recovery tower is stopped.
Preferably, the operation flow of the step 2 specifically includes:
a) After the feeding of the recovery tower is completed, an inner operator starts a steam regulating valve at the bottom of the recovery tower to heat and boost the pressure of the recovery tower, wherein the valve opening of the steam regulating valve is less than or equal to 2.5%, the regulating amplitude of the steam regulating valve is less than or equal to 1% each time, and the regulating interval time is less than or equal to 5min;
b) Then, an inner operator adjusts a recovery tower kettle steam adjusting valve and a recovery tower top refrigerant adjusting valve to maintain the pressure of the recovery tower at 0.5-0.7MPa, and total reflux operation is carried out.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the original separation process is improved, and R124 is selectively vented at the reflux temperature of 35 ℃, so that the recovery rate of R124 is improved, and meanwhile, the amounts of R133a and R134a doped in R124 are obviously reduced, so that the waste of R133a and R134a is reduced, and the recovery rates of R133a and R134a are improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the description of the embodiments will be briefly described below.
FIG. 1 is a process flow diagram of a method for separating R134a, R133a and R124 from rectified heavy components according to the present invention.
Digital description in the drawings:
1. rectifying tower bottom; 2. a rectifying column residue tank; 3. a buffer tank; 4. a R134a crude product groove; 5. r133a recovery tank; 6. a recovery tower; 7. and recovering a tower residue tank.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the following description will be made in detail with reference to the technical solutions in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments.
A clear and complete description of a process for separating R134a, R133a and R124 from a rectified heavy fraction according to the present invention will now be described with reference to the accompanying drawings.
Example 1
The invention provides a method for separating R134a, R133a and R124 from rectified heavy components, which specifically comprises the following steps:
step 1:
a) When the temperature of the rectifying tower kettle 1 is higher than 75 ℃, an inner operator opens a discharging regulating valve of the rectifying tower kettle 1 to divide the recombinant pressure in the rectifying tower raffinate tank 2 to the buffer tank 3;
b) When the liquid level of the buffer tank 3 is more than 1000mm, an inner operator informs an outer operator to open an inlet valve and an outlet valve of a refrigerant regulating valve of a condenser at the top of the recovery tower 6, a refrigerant outlet valve, a front valve and a rear valve of a steam regulating valve of the tower kettle of the recovery tower 6 and a shell side condensed water outlet valve of the tower kettle of the recovery tower 6;
d) Then an outer operator opens a front valve of a recovery tower 6 top extraction regulating valve and a regulating valve discharging valve, and an inner operator opens the recovery tower 6 top extraction regulating valve to discharge the pressure of the recovery tower 6 to 0;
e) Finally, an external operator opens a discharge valve at the bottom of the buffer tank 3 and a feeding valve at the tower kettle of the recovery tower 6, and feeds the recovery tower 6 by using the pressure difference, and stops feeding the recovery tower 6 when the liquid level of the recovery tower 6 reaches 1600 mm.
Step 2:
a) After the feeding of the recovery tower 6 is completed, an inner operator starts a steam regulating valve at the tower bottom of the recovery tower 6 to heat and boost pressure of the recovery tower 6, wherein the valve opening of the steam regulating valve is less than or equal to 2.5%, the regulating amplitude of the steam regulating valve is less than or equal to 1% each time, and the regulating interval time is less than or equal to 5min;
b) Then, the inner operator adjusts the steam adjusting valve at the bottom of the recovery tower 6 and the refrigerant adjusting valve at the top of the recovery tower 6, and the pressure of the recovery tower 6 is maintained at 0.5MPa, so as to perform total reflux operation.
Step 3: after 20 minutes of reflux, opening a channel from the top of the recovery tower 6 to the R134a crude product tank 4, and opening a recovery tower 6 top extraction regulating valve to extract R134a to 134a crude product tank to extract R134a to R134a crude product tank 4;
step 4: when the temperature of the top of the recovery tower 6 (namely the reflux temperature) reaches 30 ℃, and the temperature of the bottom of the recovery tower 6 reaches 55 ℃, opening a top emptying valve to empty R124;
step 5: when the temperature of the top of the recovery tower 6 is higher than 55 ℃, opening a channel from the recovery tower 6 to the recovery tank, and opening a recovery tower 6 top extraction regulating valve to extract R133a to the recovery tank;
step 6: when the liquid level in the recovery tower 6 is reduced to 380mm, stopping the operation of the recovery tower 6, and pressing the material in the tower bottom of the recovery tower 6 to a residual liquid tank 7 of the recovery tower;
step 7: repeating the steps, and pressing the materials in the recovery tank into the accident tank when the liquid level in the recovery tank reaches 170 cm.
The overhead blowdown components were sampled and analyzed during blowdown R124, 11 times with consistent sampling intervals. The results are shown in Table 1:
TABLE 1 analysis Chamber sample recovery column 6 overhead blowdown data at reflux temperature 30℃
| Component (A) | R134a(％) | R124(％) | R133a(％) |
| 1 | 25.1365 | 60.3145 | 3.3245 |
| 2 | 20.3648 | 61.2356 | 5.2486 |
| 3 | 13.2564 | 63.4562 | 2.5879 |
| 4 | 16.4318 | 62.315 | 3.2569 |
| 5 | 21.5698 | 72.1546 | 5.2459 |
| 6 | 18.5246 | 65.1423 | 6.3589 |
| 7 | 9.3569 | 73.1546 | 4.2598 |
| 8 | 10.2589 | 76.2156 | 7.8954 |
| 9 | 15.3269 | 75.2569 | 5.2156 |
| 10 | 13.3264 | 78.2564 | 6.0458 |
| 11 | 9.8756 | 80.2653 | 9.6589 |
| Average value of | 15.7662 | 69.797 | 5.3726 |
Example 2
The invention provides a method for separating R134a, R133a and R124 from rectified heavy components, which specifically comprises the following steps:
step 1:
a) When the temperature of the rectifying tower kettle 1 is higher than 75 ℃, an inner operator opens a discharging regulating valve of the rectifying tower kettle 1 to divide the recombinant pressure in the rectifying tower raffinate tank 2 to the buffer tank 3;
b) When the liquid level of the buffer tank 3 is more than 1000mm, an inner operator informs an outer operator to open an inlet valve and an outlet valve of a refrigerant regulating valve of a condenser at the top of the recovery tower 6, a refrigerant outlet valve, a front valve and a rear valve of a steam regulating valve of the tower kettle of the recovery tower 6 and a shell side condensed water outlet valve of the tower kettle of the recovery tower 6;
d) Then an outer operator opens a front valve of a recovery tower 6 top extraction regulating valve and a regulating valve discharging valve, and an inner operator opens the recovery tower 6 top extraction regulating valve to discharge the pressure of the recovery tower 6 to 0;
e) Finally, an external operator opens a discharge valve at the bottom of the buffer tank 3 and a feeding valve at the tower kettle of the recovery tower 6, and feeds the recovery tower 6 by using the pressure difference, and stops feeding the recovery tower 6 when the liquid level of the recovery tower 6 reaches 1600 mm.
Step 2:
a) After the feeding of the recovery tower 6 is completed, an inner operator starts a steam regulating valve at the tower bottom of the recovery tower 6 to heat and boost pressure of the recovery tower 6, wherein the valve opening of the steam regulating valve is less than or equal to 2.5%, the regulating amplitude of the steam regulating valve is less than or equal to 1% each time, and the regulating interval time is less than or equal to 5min;
b) Then, the inner operator adjusts the steam adjusting valve at the bottom of the recovery tower 6 and the refrigerant adjusting valve at the top of the recovery tower 6, and the pressure of the recovery tower 6 is maintained at 0.6MPa, so as to perform total reflux operation.
Step 3: after refluxing for 25min, opening a channel from the top of the recovery tower 6 to the R134a crude product tank 4, and opening a recovery tower 6 top extraction regulating valve to extract R134a to 134a crude product tank to extract R134a to R134a crude product tank 4;
step 4: when the temperature of the top of the recovery tower 6 reaches 35 ℃ and the temperature of the bottom of the recovery tower 6 reaches 57 ℃, opening a top emptying valve to empty R124;
step 5: when the temperature of the top of the recovery tower 6 is higher than 55 ℃, opening a channel from the recovery tower 6 to the recovery tank, and opening a recovery tower 6 top extraction regulating valve to extract R133a to the recovery tank;
step 6: when the liquid level in the recovery tower 6 is reduced to 400mm, stopping the operation of the recovery tower 6, and pressing the material in the tower bottom of the recovery tower 6 to a residual liquid tank 7 of the recovery tower;
step 7: repeating the steps, and pressing the materials in the recovery tank into the accident tank when the liquid level in the recovery tank reaches 180 cm.
The overhead blowdown components were sampled and analyzed during blowdown R124, 11 times with consistent sampling intervals. The results are shown in Table 2:
TABLE 2 analysis Chamber sample recovery column 6 overhead blowdown data at reflux temperature 35℃
| Component (A) | R134a(％) | R124(％) | R133a(％) |
| 1 | 3.6823 | 88.3132 | 5.2783 |
| 2 | 7.7346 | 73.5635 | 8.548 |
| 3 | 2.034 | 80.9405 | 3.8716 |
| 4 | 16.4318 | 71.462 | 10.7813 |
| 5 | 22.0648 | 70.8504 | 9.1708 |
| 6 | 6.343 | 83.2364 | 8.9759 |
| 7 | 9.3301 | 89.8826 | 0.6457 |
| 8 | 4.564 | 90.8228 | 2.7499 |
| 9 | 6.4526 | 87.5842 | 1.0408 |
| 10 | 2.5341 | 90.7951 | 4.1578 |
| 11 | 5.0087 | 94.5171 | 0.1397 |
| Average value of | 7.8345 | 83.8152 | 5.0327 |
Example 3
The invention provides a method for separating R134a, R133a and R124 from rectified heavy components, which specifically comprises the following steps:
step 1:
a) When the temperature of the rectifying tower kettle 1 is higher than 75 ℃, an inner operator opens a discharging regulating valve of the rectifying tower kettle 1 to divide the recombinant pressure in the rectifying tower raffinate tank 2 to the buffer tank 3;
b) When the liquid level of the buffer tank 3 is more than 1000mm, an inner operator informs an outer operator to open an inlet valve and an outlet valve of a refrigerant regulating valve of a condenser at the top of the recovery tower 6, a refrigerant outlet valve, a front valve and a rear valve of a steam regulating valve of the tower kettle of the recovery tower 6 and a shell side condensed water outlet valve of the tower kettle of the recovery tower 6;
d) Then an outer operator opens a front valve of a recovery tower 6 top extraction regulating valve and a regulating valve discharging valve, and an inner operator opens the recovery tower 6 top extraction regulating valve to discharge the pressure of the recovery tower 6 to 0;
e) Finally, an external operator opens a discharge valve at the bottom of the buffer tank 3 and a feeding valve at the tower kettle of the recovery tower 6, and feeds the recovery tower 6 by using the pressure difference, and stops feeding the recovery tower 6 when the liquid level of the recovery tower 6 reaches 1600 mm.
Step 2:
a) After the feeding of the recovery tower 6 is completed, an inner operator starts a steam regulating valve at the tower bottom of the recovery tower 6 to heat and boost pressure of the recovery tower 6, wherein the valve opening of the steam regulating valve is less than or equal to 2.5%, the regulating amplitude of the steam regulating valve is less than or equal to 1% each time, and the regulating interval time is less than or equal to 5min;
b) Then, the inner operator adjusts the steam adjusting valve at the bottom of the recovery tower 6 and the refrigerant adjusting valve at the top of the recovery tower 6, and the pressure of the recovery tower 6 is maintained at 0.7MPa, so as to perform total reflux operation.
Step 3: after refluxing for 30min, opening a channel from the top of the recovery tower 6 to the R134a crude product tank 4, and opening a recovery tower 6 top extraction regulating valve to extract R134a to 134a crude product tank to extract R134a to R134a crude product tank 4;
step 4: when the temperature of the top of the recovery tower 6 reaches 38 ℃ and the temperature of the bottom of the recovery tower 6 reaches 60 ℃, opening a top emptying valve to empty R124;
step 5: when the temperature of the top of the recovery tower 6 is higher than 55 ℃, opening a channel from the recovery tower 6 to the recovery tank, and opening a recovery tower 6 top extraction regulating valve to extract R133a to the recovery tank;
step 6: when the liquid level in the recovery tower 6 is reduced to 420mm, stopping the operation of the recovery tower 6, and pressing the material in the tower bottom of the recovery tower 6 to a residual liquid tank 7 of the recovery tower;
step 7: repeating the steps, and pressing the materials in the recovery tank into the accident tank when the liquid level in the recovery tank reaches 190 cm.
The overhead blowdown components were sampled and analyzed during blowdown R124, 11 times with consistent sampling intervals. The results are shown in Table 3:
TABLE 3 analysis Chamber sample recovery column 6 overhead blowdown data at reflux temperature 38℃
| Component (A) | R134a(％) | R124(％) | R133a(％) |
| 1 | 5.4897 | 83.3569 | 4.2356 |
| 2 | 8.5297 | 70.2658 | 8.9658 |
| 3 | 3.0214 | 76.5648 | 4.5214 |
| 4 | 17.4895 | 72.3569 | 11.259 |
| 5 | 23.1589 | 71.2548 | 9.2568 |
| 6 | 5.2648 | 81.0256 | 9.3658 |
| 7 | 10.2354 | 85.2359 | 3.2589 |
| 8 | 5.2568 | 90.0325 | 3.2598 |
| 9 | 7.1548 | 83.2359 | 2.3589 |
| 10 | 3.2459 | 88.1574 | 3.25687 |
| 11 | 5.2365 | 90.5648 | 1.2569 |
| Average value of | 8.5530 | 81.0956 | 5.54507 |
Comparative example
A method for separating R134a, R133a and R124 from a rectified heavy fraction, comprising the steps of:
step 1:
a) When the temperature of the rectifying tower kettle 1 is higher than 75 ℃, an inner operator opens a discharging regulating valve of the rectifying tower kettle 1 to divide the recombinant pressure in the rectifying tower raffinate tank 2 to the buffer tank 3;
b) When the liquid level of the buffer tank 3 is more than 1000mm, an inner operator informs an outer operator to open an inlet valve and an outlet valve of a refrigerant regulating valve of a condenser at the top of the recovery tower 6, a refrigerant outlet valve, a front valve and a rear valve of a steam regulating valve of the tower kettle of the recovery tower 6 and a shell side condensed water outlet valve of the tower kettle of the recovery tower 6;
d) Then an outer operator opens a front valve of a recovery tower 6 top extraction regulating valve and a regulating valve discharging valve, and an inner operator opens the recovery tower 6 top extraction regulating valve to discharge the pressure of the recovery tower 6 to 0;
e) Finally, an external operator opens a discharge valve at the bottom of the buffer tank 3 and a feeding valve at the tower kettle of the recovery tower 6, and feeds the recovery tower 6 by using the pressure difference, and stops feeding the recovery tower 6 when the liquid level of the recovery tower 6 reaches 1600 mm.
Step 2:
a) After the feeding of the recovery tower 6 is completed, an inner operator starts a steam regulating valve at the tower bottom of the recovery tower 6 to heat and boost pressure of the recovery tower 6, wherein the valve opening of the steam regulating valve is less than or equal to 2.5%, the regulating amplitude of the steam regulating valve is less than or equal to 1% each time, and the regulating interval time is less than or equal to 5min;
b) Then, the inner operator adjusts the steam adjusting valve at the bottom of the recovery tower 6 and the refrigerant adjusting valve at the top of the recovery tower 6, and the pressure of the recovery tower 6 is maintained at 0.6MPa, so as to perform total reflux operation.
Step 3: after refluxing for 25min, opening a channel from the top of the recovery tower 6 to the R134a crude product tank 4, and opening a recovery tower 6 top extraction regulating valve to extract R134a to 134a crude product tank to extract R134a to R134a crude product tank 4;
step 4: when the temperature of the top of the recovery tower 6 reaches 40 ℃ and the temperature of the bottom of the recovery tower 6 reaches 60 ℃, opening a top emptying valve to empty R124;
step 5: when the temperature of the top of the recovery tower 6 is higher than 40 ℃, opening a channel from the recovery tower 6 to the recovery tank, and opening a recovery tower 6 top extraction regulating valve to extract R133a to the recovery tank;
step 6: when the liquid level in the recovery tower 6 is reduced to 400mm, stopping the operation of the recovery tower 6, and pressing the material in the tower bottom of the recovery tower 6 to a residual liquid tank 7 of the recovery tower;
step 7: repeating the steps, and pressing the materials in the recovery tank into the accident tank when the liquid level in the recovery tank reaches 180 cm.
The overhead blowdown components were sampled and analyzed during blowdown R124, 11 times with consistent sampling intervals. The results are shown in Table 4:
TABLE 4 analysis Chamber sample recovery column 6 overhead blowdown data at 40 ℃ reflux temperature
| Component (A) | R134a(％) | R124(％) | R133a(％) |
| 1 | 2.6758 | 81.3175 | 13.2805 |
| 2 | 0.7631 | 11.5635 | 77.5195 |
| 3 | 0.8408 | 5.9405 | 80.0648 |
| 4 | 36.4318 | 61.462 | 0.7813 |
| 5 | 42.0648 | 53.8504 | 3.1708 |
| 6 | 16.9795 | 73.2364 | 8.3394 |
| 7 | 98.9733 | 0.8826 | 0.0025 |
| 8 | 14.2917 | 74.8228 | 9.0222 |
| 9 | 0.6048 | 64.5842 | 29.8886 |
| 10 | 3.3617 | 78.7951 | 15.3302 |
| 11 | 3.065 | 95.5171 | 1.0834 |
| Average value of | 20.0048 | 54.7247 | 21.6803 |
As can be seen from the analysis of the data in tables 1 to 4, when the technical scheme of the invention is adopted to separate R134a, R124 and R133a, the amount of the separated R124 is significantly improved, and especially when the reflux temperature is 35 ℃, the recovery rate of R124 is improved from 54.7% to 87.6% of the original process; and wherein the amount of doped R133a and R134a is significantly reduced, thereby reducing the waste of R133a and R134a.
Based on the above results, further sampling analysis was performed on the overhead components with the reflux temperature at 35 degrees and the pressure of the recovery column 6 maintained at 0.5MPa and 0.7MPa, respectively, and the results are shown in tables 5 and 6:
TABLE 5 analysis chamber sample recovery column 6 overhead blowdown composition data at reflux temperature 35℃and pressure 0.5MPa
| Component (A) | R134a(％) | R124(％) | R133a(％) |
| 1 | 56.324 | 38.643 | 4.033 |
| 2 | 65.4634 | 30.5635 | 2.9731 |
| 3 | 62.1234 | 33.4329 | 3.4437 |
| 4 | 80.5008 | 17.5549 | 0.9443 |
| 5 | 55.0648 | 40.8504 | 3.0848 |
| 6 | 59.3343 | 38.2364 | 1.4293 |
| 7 | 57.9987 | 38.8826 | 2.1187 |
| 8 | 58.2341 | 24.2365 | 1.2456 |
| 9 | 55.1247 | 19.2568 | 3.2658 |
| 10 | 53.2689 | 31.2546 | 4.2568 |
| 11 | 72.1356 | 36.2589 | 4.1256 |
| Average value of | 61.4157 | 31.7428 | 2.8110 |
TABLE 6 analysis chamber sample recovery column 6 overhead blowdown composition data at reflux temperature 35℃and pressure 0.7MPa
As can be seen from the analysis of the data in tables 2, 5 and 6, when the reflux temperature was 35 degrees and the pressure in the recovery column 6 was maintained at 0.6MP, the R124 was vented, and the recovery rate of R124 was significantly improved and the waste of resources was reduced.
Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention.
Claims (1)
1. A process for separating R134a, R133a and R124 from a rectified heavy fraction, characterized by: the method comprises the following operation steps:
step 1: pressing heavy components in a residual liquid tank of the rectifying tower to a buffer tank, and feeding the heavy components into a recovery tower from the buffer tank;
step 2: heating and boosting the recovery tower, maintaining the pressure of the recovery tower at 0.6MPa, and performing total reflux operation;
step 3: after 20-30min of reflux, opening a channel from the top of the recovery tower to the R134a crude product tank, and opening a recovery tower top extraction regulating valve to extract R134a to R134a crude product tanks from the R134a to the R134a crude product tank;
step 4: when the temperature of the top of the recovery tower reaches 35 ℃, and the temperature of the bottom of the recovery tower reaches 55-60 ℃, opening a top emptying valve to empty R124;
step 5: when the temperature of the top of the recovery tower is higher than 55 ℃, opening a channel from the recovery tower to the recovery tank, and opening a recovery tower top extraction regulating valve to extract R133a to the recovery tank;
step 6: when the liquid level in the recovery tower is reduced to 400mm, stopping operation of the recovery tower, and pressing the materials in the bottom of the recovery tower to a residual liquid tank of the recovery tower;
step 7: repeating the steps, and pressing the materials in the recovery tank into the accident tank when the liquid level in the recovery tank reaches 180 cm;
the operation flow of the step 1 specifically comprises the following steps:
a) When the temperature of the rectifying tower kettle is higher than 75 ℃, an inner operator opens a discharging regulating valve of the rectifying tower kettle to divide the recombinant pressure in the rectifying tower residual liquid tank to a buffer tank;
b) When the liquid level of the buffer tank is more than 1000mm, an inner operator informs an outer operator to open an inlet valve and an outlet valve of a refrigerant regulating valve of a condenser at the top of the recovery tower, a refrigerant outlet valve, front and rear valves of a steam regulating valve of the recovery tower kettle and a condensed water outlet valve of a shell side of the recovery tower kettle;
d) Then an outer operator opens a front valve of a recovery tower top extraction regulating valve and a regulating valve discharging valve, and an inner operator opens the recovery tower top extraction regulating valve to discharge the pressure of the recovery tower to 0;
e) Finally, an external operator opens a discharge valve at the bottom of the buffer tank and a feed valve at the bottom of the recovery tower, and feeds the recovery tower by using the pressure difference, and stops feeding the recovery tower when the liquid level of the recovery tower reaches 1600 mm;
the operation flow of the step 2 specifically comprises the following steps:
a) After the feeding of the recovery tower is completed, an inner operator starts a steam regulating valve at the bottom of the recovery tower to heat and boost the pressure of the recovery tower, wherein the valve opening of the steam regulating valve is less than or equal to 2.5%, the regulating amplitude of the steam regulating valve is less than or equal to 1% each time, and the regulating interval time is less than or equal to 5min;
b) Then, an inner operator adjusts a recovery tower kettle steam adjusting valve and a recovery tower top refrigerant adjusting valve to maintain the pressure of the recovery tower at 0.6MPa, and total reflux operation is performed.
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