CN113499663A - Resource treatment and recovery method for shale oil dry distillation refining waste gas - Google Patents
Resource treatment and recovery method for shale oil dry distillation refining waste gas Download PDFInfo
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- CN113499663A CN113499663A CN202110914082.0A CN202110914082A CN113499663A CN 113499663 A CN113499663 A CN 113499663A CN 202110914082 A CN202110914082 A CN 202110914082A CN 113499663 A CN113499663 A CN 113499663A
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- waste gas
- shale oil
- dry distillation
- aromatic hydrocarbon
- resin
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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
- B01D53/002—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 condensation
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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
- B01D53/04—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 with stationary adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
- B01D2257/7022—Aliphatic hydrocarbons
Abstract
The invention discloses a resource treatment and recovery method for shale oil dry distillation refining waste gas, which comprises the steps of condensing waste gas containing light hydrocarbon, aromatic hydrocarbon and the like generated by shale oil dry distillation refining, enabling the waste gas to pass through a fixed bed adsorption column filled with macroporous aromatic hydrocarbon ethylene adsorption resin to enable the light hydrocarbon and the aromatic hydrocarbon to be adsorbed on the adsorption resin, blowing off the adsorption saturated resin through low-pressure steam, condensing the blown-off light hydrocarbon and aromatic hydrocarbon through a spiral plate heat exchanger, layering an oil-water separator and recycling the light hydrocarbon and the aromatic hydrocarbon. The invention recycles the light hydrocarbon and aromatic hydrocarbon waste gas by resource treatment of shale oil dry distillation refining, and more than 95 percent of light hydrocarbon and aromatic hydrocarbon are recycled, thereby realizing the unification of waste gas treatment and resource utilization, simultaneously avoiding the coking phenomenon generated in the dry distillation process to influence the production, and having great benefit for shale oil dry distillation oil-making enterprises in China.
Description
Technical Field
The invention belongs to the technical field of resource treatment and recycling of petrochemical shale oil dry distillation refining waste gas, and particularly relates to a method for adsorbing light hydrocarbon and aromatic hydrocarbon in waste gas by using macroporous adsorption resin, so that shale oil dry distillation refining waste gas is desorbed and recycled to be reused in production, and the production cost is reduced.
Background
Shale oil refers to a petroleum resource contained in a shale layer system mainly composed of shale. Including oil in shale pores and fractures, and also including oil resources in tight carbonate or clastic adjacent layers and interbedded layers in shale layer systems.
The development modes which are usually effective are horizontal well and staged fracturing technology. In the field of solid mineral products, shale oil is artificial petroleum and is a brown viscous liquid product with special pungent smell generated by the thermal decomposition of organic substances during the dry distillation of shale. The method for preparing light oil from shale oil is the one with the lowest cost in the method for preparing qualified liquid fuel from artificial petroleum. The exploited shale is subjected to carbonization and refining to obtain petroleum, and then is cracked to obtain light oil, aromatic hydrocarbon, paraffin oil and the like with various components, so that the condition of shortage of crude oil in China is supplemented, waste gas is generated in the carbonization process, one part of the waste gas is used as heating gas to continue carbonization, the other part of the waste gas is directly discharged and combusted, resources are wasted, and meanwhile, the waste gas is coked when being used as carbonization heating gas, so that the coking in the carbonization furnace influences the heating efficiency, and further influences the production yield.
Disclosure of Invention
The invention aims to provide a method for resource treatment and recovery of shale oil dry distillation refining waste gas, which has the advantages of simple operation, lower cost and controllable temperature, and can recover light hydrocarbon and aromatic hydrocarbon in the waste gas for recycling and reduce the phenomenon of coking in a dry distillation furnace.
Aiming at the purposes, the technical scheme adopted by the invention comprises the following steps:
1. after shale oil dry distillation refining waste gas is condensed, the obtained waste gas passes through a macroporous aromatic hydrocarbon ethylene adsorption resin column under the condition that the flow speed is 100-500 BV/h.
2. And blowing off the resin column adsorbed with the shale oil dry distillation refining waste gas by using low-pressure steam of 110-130 ℃ and 0.01-0.1 MPa.
3. The stripped shale oil dry distillation refining waste gas and steam are condensed by a spiral plate heat exchanger, and light hydrocarbon and aromatic hydrocarbon substances are recovered by layering of condensate through an oil-water separator.
4. And leaching the desorbed resin column with distilled water, reducing the temperature of the resin, and reusing the resin.
In the step 1, the obtained waste gas preferably passes through a macroporous aromatic hydrocarbon ethylene adsorption resin column under the condition that the flow rate is 300-400 BV/h.
The macroporous aromatic hydrocarbon vinyl adsorption resin is Innovate-30 macroporous adsorption resin (provided by Xian Jinwatite environmental protection science and technology Co., Ltd.), has good effect, can meet the emission requirement, simultaneously carries out a large number of comparison experiments on the macroporous resin in the current market, such as Amberlite XDA-7 macroporous adsorption resin, Amberlite XDA-4 macroporous adsorption resin (provided by Tao chemical China Co., Ltd.), XDA-1 macroporous adsorption resin (provided by Xian electric resin factory), carries out comparison experiments on the flow rate, the selection of eluent, the blow-off temperature and the like, and preferably selects Innovate-30 macroporous adsorption resin.
In the step 2, the flow rate of the low-pressure steam is preferably 10-500 kg/h. Specifically, the steam flow is specifically considered according to the actual resin filling amount, for example, the resin filling amount is 40 liters, the steam flow can be 30-50 kg/h, the resin filling amount is 3 cubic meters, and the steam flow can be 300-400 kg/h.
The invention utilizes a resin adsorption method to carry out resource treatment and recovery on light hydrocarbon and aromatic hydrocarbon in the shale oil dry distillation refining waste gas, uses low-pressure steam to blow off and regenerate the resin, carries out oil-water separation to recover the light hydrocarbon and the aromatic hydrocarbon, then uses water to spray the resin for cooling, and carries out resin re-adsorption. Finally, light hydrocarbon and aromatic hydrocarbon are recovered, and the coking phenomenon in production is reduced. Compared with the prior art, the invention has the following beneficial effects:
1. the invention has simple process, single and less raw material investment, lower cost and obvious effect of recovering light hydrocarbon and aromatic hydrocarbon, greatly reduces the content of light hydrocarbon and aromatic hydrocarbon in the waste gas, can recover the products in the waste gas and reduces the atmospheric pollution and the coking phenomenon of the gas retort.
2. The invention improves the dry distillation efficiency of the retort furnace, saves energy and can be recycled after adsorption stripping condensation.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
The shale oil dry distillation refining waste gas of a certain petrochemical company Limited, wherein the content of light hydrocarbon and aromatic hydrocarbon is 6100mg/Nm3The specific recovery method is as follows:
1. light hydrocarbon and aromatic hydrocarbon generated by dry distillation and refining of shale oil in dry distillation furnaceAfter the aromatic waste gas is condensed, the obtained waste gas has the flow rate of 12Nm3The air is passed through a resin column filled with 40LInnovate-30 macroporous adsorption resin under the condition of/h, and the air inlet time is 18 h.
2. And blowing off the resin column adsorbed with the shale oil dry distillation refining waste gas by using low-pressure steam with the temperature of 112-115 ℃ and the pressure of 0.09MPa at the flow rate of 50 kg/h.
3. The stripped shale oil dry distillation refining waste gas and steam are condensed by a spiral plate heat exchanger, and light hydrocarbon and aromatic hydrocarbon substances are recovered by layering of condensate through an oil-water separator.
4. And leaching the desorbed resin column with distilled water, reducing the temperature of the resin, and reusing the resin.
The upper layer oil recovered by layering through the oil-water separator was detected by high performance liquid chromatography, and the results are shown in table 1.
TABLE 1 shale oil destructive distillation refining waste gas recovery effect
| Sequence of | N-alkanes of formula (I) | Isoalkanes I | Olefin O | Cycloalkane N | Aromatic hydrocarbons A | The sum of lines | NoPeakA％(m/m) |
| C1 | |||||||
| C2 | |||||||
| C3 | |||||||
| C4 | 0.024 | 0.024 | |||||
| C5 | 0.026 | 0.04 | 0.066 | 0.064 | |||
| C6 | 0.116 | 0.303 | 33.207 | 33.626 | 0.033 | ||
| C7 | 0.345 | 1.969 | 0.529 | 9.334 | 12.177 | 0.032 | |
| C8 | 0.743 | 0.579 | 1.352 | 5.959 | 8.633 | 0.336 | |
| C9 | 1.21 | 15 | 0.146 | 2.104 | 2.875 | 21.335 | 0.373 |
| C10 | 1.643 | 2.111 | 0.121 | 1.485 | 5.454 | 10.814 | 0.448 |
| C11 | 1.66 | 1.921 | 4.173 | 0.733 | 8.487 | 0.33 | |
| C12 | 4.837 | 4.837 | 0.125 | ||||
| C13 | |||||||
| C14 | |||||||
| Column sum | 5.743 | 19.611 | 2.603 | 9.643 | 62.399 | 99.999 | 1.741 |
As can be seen from Table 1, after the waste gas is treated by Innovate-30 adsorption resin and blown off, C6-C12 organic matters can be recovered, the recovered organic matters are layered and weighed to be about 1.29kg, the recovery rate of light hydrocarbon and aromatic hydrocarbon can reach 97.90 percent, and the recovered organic matters can be directly reused in production.
Example 2
In step 1 of this example, the exhaust gas was obtained at a flow rate of 15Nm3Passing through a resin column filled with 40LInnovate-30 macroporous adsorption resin under the condition of/h. The other steps are the same as in example 1. The results of HPLC analysis of the upper layer of oil recovered by separation in the oil-water separator are shown in Table 2.
TABLE 2 shale oil destructive distillation refining waste gas recovery effect
| Sequence of | N-alkanes of formula (I) | Isoalkanes I | Olefin O | Cycloalkane N | Aromatic hydrocarbons A | The sum of lines | NoPeakA％(m/m) |
| C1 | |||||||
| C2 | |||||||
| C3 | |||||||
| C4 | 0.009 | 0.013 | 0.023 | 0.045 | 0.014 | ||
| C5 | 0.135 | 0.257 | 0.162 | 0.554 | 0.038 | ||
| C6 | 0.607 | 1.512 | 0.675 | 0.234 | 33.248 | 36.276 | 0.017 |
| C7 | 0.705 | 3.925 | 0.563 | 0.266 | 10.588 | 16.047 | 0.052 |
| C8 | 0.837 | 1.988 | 0.03 | 1.692 | 9.227 | 13.774 | 0.421 |
| C9 | 1.184 | 8.98 | 0.446 | 1.94 | 4.659 | 17.209 | 0.529 |
| C10 | 1.319 | 1.499 | 0.105 | 1.882 | 5.344 | 10.149 | 0.411 |
| C11 | 1.093 | 0.996 | 1.556 | 0.469 | 4.114 | 0.199 | |
| C12 | 1.829 | 1.829 | 0.085 | ||||
| C13 | |||||||
| C14 | |||||||
| Column sum | 5.889 | 19.17 | 2.004 | 7.57 | 65.364 | 99.997 | 1.766 |
As can be seen from Table 2, after the waste gas is treated by Innovate-30 adsorption resin and blown off, C6-C12 organic matters can be recovered, the recovered organic matters are layered and weighed to be about 1.28kg, the recovery rate of light hydrocarbon and aromatic hydrocarbon can reach 97.15%, and the recovered organic matters can be directly reused in production.
The results show that the shale oil dry distillation refining waste gas recovery effect is obvious, and the shale oil dry distillation refining waste gas recovery method can be popularized in a large range in industries such as shale oil and the like so as to achieve double harvest of economic benefits and environmental benefits.
Claims (4)
1. A resource treatment and recovery method for shale oil dry distillation refining waste gas is characterized by comprising the following steps:
(1) condensing shale oil dry distillation refining waste gas, and allowing the obtained waste gas to pass through a macroporous aromatic hydrocarbon ethylene adsorption resin column at the flow rate of 100-500 BV/h;
(2) blowing off the resin column adsorbed with the shale oil dry distillation refining waste gas by using low-pressure steam with the temperature of 110-130 ℃ and the pressure of 0.01-0.1 MPa;
(3) condensing the blown shale oil dry distillation refining waste gas and steam through a spiral plate heat exchanger, and layering and recovering light hydrocarbon and aromatic hydrocarbon substances from condensate through an oil-water separator;
(4) and leaching the desorbed resin column with distilled water, reducing the temperature of the resin, and reusing the resin.
2. The resource treatment and recovery method for the shale oil retorting refining waste gas according to claim 1, characterized in that: in the step (1), the obtained waste gas passes through a macroporous aromatic hydrocarbon ethylene adsorption resin column under the condition that the flow rate is 300-400 BV/h.
3. The resource treatment and recovery method for the shale oil retorting refining waste gas according to claim 1 or 2, characterized in that: the macroporous aromatic hydrocarbon vinyl adsorption resin is Innovate-30 macroporous adsorption resin.
4. The method for resource treatment and recovery of shale oil retorting refining waste gas according to claim 1, characterized in that: in the step (2), the flow rate of the low-pressure steam is 10-500 kg/h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527024A (en) * | 1968-11-05 | 1970-09-08 | Black Sivalls & Bryson Inc | Process for recovering condensible components from a gas stream |
| CN1562733A (en) * | 2004-03-25 | 2005-01-12 | 南京大学 | Method for refining hydrochloric acid as byproduct in procedure for producing chemical products of chlorinated hydrocarbons |
| CN101200286A (en) * | 2007-12-05 | 2008-06-18 | 南京大学 | Method for refining byproduct hydrogen chloride during production process of organochlorine products |
| CN104845657A (en) * | 2015-06-03 | 2015-08-19 | 西南化工研究设计院有限公司 | Purification system and process for recycling residual light oil in shale oil dry distillation tail gas |
| CN205613244U (en) * | 2016-05-05 | 2016-10-05 | 江苏建康职业学院 | Chemical production tail gas recovery processing device |
-
2021
- 2021-08-10 CN CN202110914082.0A patent/CN113499663A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3527024A (en) * | 1968-11-05 | 1970-09-08 | Black Sivalls & Bryson Inc | Process for recovering condensible components from a gas stream |
| CN1562733A (en) * | 2004-03-25 | 2005-01-12 | 南京大学 | Method for refining hydrochloric acid as byproduct in procedure for producing chemical products of chlorinated hydrocarbons |
| CN101200286A (en) * | 2007-12-05 | 2008-06-18 | 南京大学 | Method for refining byproduct hydrogen chloride during production process of organochlorine products |
| CN104845657A (en) * | 2015-06-03 | 2015-08-19 | 西南化工研究设计院有限公司 | Purification system and process for recycling residual light oil in shale oil dry distillation tail gas |
| CN205613244U (en) * | 2016-05-05 | 2016-10-05 | 江苏建康职业学院 | Chemical production tail gas recovery processing device |
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