CN106995720A - A kind of liquid phase dechlorination method of chloride alkylate oil - Google Patents
A kind of liquid phase dechlorination method of chloride alkylate oil Download PDFInfo
- Publication number
- CN106995720A CN106995720A CN201610052334.2A CN201610052334A CN106995720A CN 106995720 A CN106995720 A CN 106995720A CN 201610052334 A CN201610052334 A CN 201610052334A CN 106995720 A CN106995720 A CN 106995720A
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- CN
- China
- Prior art keywords
- chloride
- oil
- dechlorination
- hcl
- alkylate oil
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/14—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including at least two different refining steps in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention provides a kind of liquid phase dechlorination method of chloride alkylate oil, this method comprises the following steps：(1) liquid-phase hydrogenatin：Under hydroconversion condition, chloride alkylate oil is generated into the hydrogenation products containing HCl under liquid phase state with hydrogen and hydrogenation catalyst reaction；(2) liquid phase adsorption：The hydrogenation products containing HCl are contacted under liquid phase state with adsorbent, after absorption HCl, obtain removing the hydrogenation products after HCl；(3) Oil-gas Separation：By the hydrogenation products and Hydrogen Separation after the removing HCl, dechlorination alkylate oil is obtained.The integration method uses liquid-phase hydrogenatin, and its operating condition is gentle, and hydrogen-oil ratio is low, it is not necessary to sets the equipment such as hydrogenation charging heating furnace, reduces investment and the operating cost of device, it is possible to achieve the complete conversion of organochlorine.
Description
Technical field
The present invention relates to alkylate oil dechlorination field, further say, be to be related to a kind of liquid phase of integration
The liquid phase dechlorination method of the chloride alkylate oil of hydrogenation, liquid phase adsorption and Oil-gas Separation.
Background technology
Alkylate oil is a kind of common high-knock rating gasoline blend component, high with octane number, sensitive
Spend, steam is forced down, boiling spread is wide, not olefin-containing and the advantages of aromatic hydrocarbons and combustion cleaning, one
As generated by the chain reaction of isoparaffin and alkene.Current gasoline standard is improved constantly, in gasoline
Aromatic hydrocarbons and olefin(e) centent limitation are gradually strict, and the importance of alkylate oil is increasingly highlighted.With technology
Development, can introduce chlorohydrocarbon component in some cases in alkylate oil.If this kind of alkylate oil is straight
Connect as fuel combustion, unfavorable accessory substance such as HCl can be generated, so as to cause corrosion.Therefore, from
It is necessary that organic chloride is removed in this kind of alkylate oil.
Common are the removing of machine chlorine mainly has adsorbing and removing method, phase transfer catalyst removal method and hydrogenation de-
Division etc..Wherein removal method solid absorbent is because its organochlorine adsorption capacity is limited and is needed frequently again
It is raw, add the difficulty and cost of technological operation；Phase transfer catalyst removal method used catalyst price
It is of a relatively high；Hydrogenation and removing method relative maturity, but running cost is higher, equipment is more complicated.
The distillate that common oil product dechlorination is processed mainly for crude oil or crude oil, such as patent CN
103571521A discloses a kind of removing oil product such as naphtha, gasoline, diesel oil, kerosene, wax oil, original
The method of the chlorine-containing organic compounds of oil or biomass oil plant, is mixed into using dechlorination agent solution and oil product
Row dechlorination reaction, then pass through the oil product after isolated dechlorination.In addition, also having for utilizing damaged tire
The organochlorine removing of pyrolysis fuel oil and the various industrial waste oils of recovery, such as patent CN
The method that 103980938A discloses a kind of plastic containing chlorine oil production clean fuel, using catalytic distillation-
The method of low pressure liquid-phase hydrogenatin dechlorination-washing-hydrogenation upgrading-air-distillation, has obtained high-quality petrol and diesel oil
Target product, realize plastic containing chlorine oil recycling.
At present, the dechlorination of the alkylate oil for being produced with isoparaffin and alkene by chain reaction is ground
Study carefully less.Domestic patent associated therewith is such as：
CN103025687A discloses a kind of side of the hydrogenation-dechlorination of hydrocarbon products derived from ionic liquid
Method.By one or more hydrocarbon products hydrogenation-dechlorinations derived from ionic liquid-catalyzed hydrocarbon conversion reaction, so that
There is provided dechlorination product and the waste gas containing HCl, the chloride content of gained dechlorination product is less than
50ppm, typically less than 10ppm.
CN103270007A discloses a kind of method of hydrocarbon products catalysis dechlorination.By making to produce comprising hydrocarbon
Thing and the mixture of carrier gas are contacted with dechlorination catalyst under catalytic condition, are produced with providing dechlorinated hydrocarbon
Thing, HCl and carrier gas.Then by separating to provide liquid fuel or lubricating base oil.Gained dechlorination
Second chlorinity of hydrocarbon products is lower than the first chlorinity of hydrocarbon products by least 20%.
The current subject matter of chloride alkylate oil dechlorination process including the above method is that dechlorination effect has
It is to be strengthened.The former dechlorination effect can reach typically smaller than 10ppm, and the latter fills into catalysis dechlorination
The content of organic chloride for the hydrocarbon products put typically larger than 50ppm, the chlorinity of hydrocarbon products compares dechlorination after dechlorination
It is preceding low by least 20%.In addition, CN103025687A technique contains after needing gas liquid separation, separation
HCl dechlorination product may subsequently need to carry out further stripping processing；CN103270007A is de-
Carrier gas may be needed in chlorine process.
The content of the invention
In order to solve produced problem in the prior art, the invention provides a kind of liquid-phase hydrogenatin of integration,
The alkylate oil dechlorination method of liquid phase adsorption and Oil-gas Separation.The integration method uses liquid-phase hydrogenatin, its
Operating condition is gentle, and hydrogen-oil ratio is low, it is not necessary to sets the equipment such as hydrogenation charging heating furnace, reduces device
Investment and operating cost, it is possible to achieve the complete conversion of organochlorine.
To achieve these goals, the present invention provides a kind of liquid phase dechlorination method of chloride alkylate oil,
This method comprises the following steps：
(1) liquid-phase hydrogenatin：Under hydroconversion condition, by chloride alkylate oil under liquid phase state with hydrogen
With hydrogenation products of the hydrogenation catalyst reaction generation containing HCl；
(2) liquid phase adsorption：The hydrogenation products containing HCl are contacted under liquid phase state with adsorbent,
Adsorb after HCl, obtain removing the hydrogenation products after HCl；
(3) Oil-gas Separation：By the hydrogenation products and Hydrogen Separation after the removing HCl, dechlorination is obtained
Alkylate oil.
Preferably, the chloride content of the chloride alkylate oil is not more than 500ppm, the dechlorination alkane
The chloride content of base carburetion is less than 2ppm.
Preferably, the chloride alkylate oil includes at least one C4-C12Straight or branched saturated hydrocarbons
Component and at least one chlorine-containing components, not comprising unsaturated hydrocarbons component.The unsaturated hydrocarbons component is alkene
Hydrocarbon, aromatic hydrocarbons etc..The straight or branched saturated hydrocarbon component is mainly isooctane and its isomers.It is described
The research octane number (RON) of chloride alkylate oil should be greater than 90, and motor octane number should be greater than 85.
Preferably, the chlorine-containing components are organic chloride.Predominantly chloralkane.
Preferably, at least one component of the saturated hydrocarbons of the chloride alkylate oil is by isoparaffin
Generated with the alkylated reaction of alkene.Reaction can be by that can provide Hydrogen Proton H+Catalyst, it is described
The catalyst such as concentrated sulfuric acid, hydrofluoric acid, ionic liquid or solid acid etc..
Preferably, before the step (1), chloride alkylate oil and hydrogen are carried out in a mixer
After premix, temperature needed for temperature is risen into hydrogenation reaction by heater or heat exchanger enters from bottom
Liquid-phase hydrogenatin unit.Liquid-phase hydrogenatin reaction condition is gentle, and heat exchanger or heater can meet requirement,
The heating furnace of high energy consumption need not be set.
Preferably, the reaction bed temperature in the step (1) is 120-300 DEG C, reaction pressure
For 1.0-3.0MPa, charging liquid hourly space velocity (LHSV) is 1-100h-1, hydrogen to oil volume ratio is 1-20.
According to the present invention, hydrogenation catalyst described in step (1) can add for the various of this area routine
Hydrogen catalyst, it is preferable that hydrogenation catalyst described in step (1) is containing precious metals pt and/or Pd
Catalyst.Under the operating condition of mitigation, the hydrogenation catalyst can be by chloride alkylate oil
Chloride is completely converted into hydrogen chloride.
Preferably, adsorbent described in step (2) is solid absorbent.
Preferably, the adsorbent is high-temperature dechlorinating agent, and the adsorbent amount can be according to selected
The chlorosity of high-temperature dechlorinating agent is determined.According to the present invention, those skilled in the art can be true as needed
Determine the suitable consumption of adsorbent.Hydrogenation products containing HCl described in step (2) are drawn from reactor top,
Enter liquid phase adsorption unit from bottom.
Preferably, adsorption temp is 120-300 DEG C in the step (2), and adsorptive pressure is 1.0-3.0MPa.
Preferably, pressure is 1.0-2.0MPa in the step (3).The Oil-gas Separation of step (3)
This area conventional technical means can be used, it is for instance possible to use board-like fractionating column, light component such as hydrogen
Drawn by tower top and deliver to fuel gas pipe network, bottom product is dechlorination alkylate oil, the dechlorination alkylation
Oil can be cooled down directly as product carrying device, can also be exchanged heat, carried with liquid-phase hydrogenatin raw material
High-energy utilization rate.
Preferably, the dechlorination alkylate oil described in step (3) should include at least one C4-C12Straight chain
Or branched-chain saturated hydrocarbon component, predominantly isooctane and its isomers.The research of the dechlorination alkylate oil
Method octane number should be greater than 90, and motor octane number should be greater than 85.
The liquid-phase hydrogenatin reaction condition of the present invention is gentle, and heat exchanger or heater can meet requirement, no
Need the heating furnace of setting high energy consumption.
Compared with prior art, the advantage of the invention is that：
1st, liquid phase hydrogenation technology is employed, reaction condition is gentle, and hydrogen-oil ratio is small, eliminates hydrogenation charging
Heating furnace, reduces equipment investment and operating cost.
2nd, high-temperature liquid-phase absorption avoids the dew point corrosion as caused by water that may be present, extends device
Life-span, reduce unnecessary heat transmission equipment.
3rd, the first adsorbing and removing HCl of liquid-phase hydrogenatin product, then the H wherein contained is removed by Oil-gas Separation2,
The HCl carried in liquid-phase hydrogenatin product can be removed by adsorbent as far as possible.
4th, the alkylate oil dechlorination method integrated by the present invention, can contain the chloride of alkylate oil
Amount be down to the octane number of alkylate oil before and after below 2ppm, and dechlorination, do, the ginseng such as Lei Shi vapour pressures
Number keeps constant.
Other features and advantages of the present invention will give specifically in subsequent embodiment part
It is bright.
Brief description of the drawings
Fig. 1 shows the process flow diagram according to one embodiment of the present invention.
Description of reference numerals
The chloride alkylate oils of 1-, the new hydrogen of 2-, 3- hydrogenation entry mixers, 4- hydrogenation charging, 5- be hydrogenated with into
Expect heater/heat exchanger, 6- hydrogenation is fed, 7- liquid-phase hydrogenatin units, hydrogenation logistics of the 8- containing HCl,
9- liquid phase adsorption units, 10- removes HCl hydrogenation products, 11- Oil-gas Separation units, 12- hydrogens
Hydro carbons, 13- dechlorination alkylate oils
Embodiment
The preferred embodiment of the present invention is described in more detail below.These embodiments be provided be for
Make the present invention more thorough and complete, and can will fully convey the scope of the invention to ability
The technical staff in domain.
Embodiment 1
Chloride alkylate oil 1 enters hydrogenation feed heater/heat exchanger 5 under the injection of the new air-flow of hydrogen 2,
150 DEG C of temperature needed for hydrogenation reaction is heated in the presence of thermal source.Then go through liquid-phase hydrogenatin list
Member 7, makes organic chloride and hydrogen react hydrogenation logistics 8 of the generation containing HCl, hydrogenation catalyst be containing
Pt-Pd catalyst.Hydrogenation logistics 8 containing HCl enters liquid phase adsorption unit 9 from bottom, passes through absorption
Agent is that antichlor KT405 suction-operated removes the HCl included in the hydrogenation logistics 8 containing HCl.It is de-
Except HCl hydrogenation products 10 subsequently enter Oil-gas Separation unit 11, dechlorination alkylate oil 13 is isolated
With hydrogen hydro carbons 12.Wherein dechlorination alkylate oil 13 can be used as product carrying device, hydrogen hydrocarbon
Class 12 then sends into the fuel gas pipe network of factory.
Using the process chart shown in Fig. 1, by the liquid-phase hydrogenatin of an integration, liquid phase adsorption and
Oil-gas Separation technique removes the organochlorine component in chloride alkylate oil.Liquid-phase hydrogenatin, liquid phase adsorption and
The technological condition of Oil-gas Separation unit is listed in table 1 to table 3 respectively.
The liquid-phase hydrogenatin cell process condition of table 1
| Reactor pressure/MPa | 2.0 |
| Reaction bed temperature/DEG C | 150 |
| Volume space velocity (fresh feed)/h-1 | 5.0 |
| Reactor inlet standard state hydrogen to oil volume ratio | 10 |
The liquid phase adsorption cell process condition of table 2
| Absorber pressure/MPa | 2.0 |
| Adsorbent bed temperature/DEG C | 150 |
The Oil-gas Separation cell process condition of table 3
| Separate mode | Fractionating column |
| Operating pressure/MPa | 2.0 |
| Overhead product | Hydrogen |
| Bottom product | Dechlorination alkylate oil |
Test case 1
The main character of the chloride alkylate oil 1 of above-described embodiment, dechlorination alkylate oil 13 is surveyed
Examination, test result is listed in table 4 and table 5 respectively.
The main character of the chloride alkylate oil 1 of table 4
The main character of the dechlorination alkylate oil 13 of table 5
| Detection project | Measured value |
| Density (15.5 DEG C)/(kg/m3) | 689 |
| Mechanical admixture/wt% | Nothing |
| Research octane number (RON) (RON) | 95 |
| Motor octane number (MON) | 92 |
| Lei Shi vapour pressures (RVP)/MPa | 0.042 |
| Do/DEG C | 197 |
| Content of organic chloride/ppm in alkylate oil | ~1 |
, can completely effectively will be chloride by method of the present invention it can be seen from embodiment
Organic chlorohydrocarbon in alkylate oil is removed to about 1ppm from 300ppm, so as to largely avoid
The adverse effect that chloride alkylate oil is brought when as fuel combustion.Alkylate oil is pungent before and after dechlorination
Alkane value, do, the parameter such as Lei Shi vapour pressures keeps constant, whole dechlorination process is to the pungent of alkylate oil
The properties such as alkane value do not influence.In addition, whole integrated process operation temperature and pressure are relatively low, no
Hydrogenation charging heating furnace is needed, operating cost is reduced while reduction equipment investment.
It is described above various embodiments of the present invention, described above is exemplary, and exhaustive
Property, and it is also not necessarily limited to disclosed each embodiment.In the model without departing from illustrated each embodiment
Enclose and spirit in the case of, many modifications and changes for those skilled in the art
It will be apparent from.
Claims (10)
1. a kind of liquid phase dechlorination method of chloride alkylate oil, it is characterised in that this method include with
Lower step：
(1) liquid-phase hydrogenatin：Under hydroconversion condition, by chloride alkylate oil under liquid phase state with hydrogen
With hydrogenation products of the hydrogenation catalyst reaction generation containing HCl；
(2) liquid phase adsorption：The hydrogenation products containing HCl are contacted under liquid phase state with adsorbent,
Obtain removing the hydrogenation products after HCl；
(3) Oil-gas Separation：By the hydrogenation products and Hydrogen Separation after the removing HCl, dechlorination is obtained
Alkylate oil.
2. according to the method described in claim 1, wherein, the chloride of the chloride alkylate oil contains
Amount is not more than 500ppm, and the chloride content of the dechlorination alkylate oil is less than 2ppm.
3. method according to claim 2, wherein, the chloride alkylate oil includes at least one
Plant C4-C12Straight or branched saturated hydrocarbon component and at least one chlorine-containing components, not comprising unsaturated hydrocarbons
Component.
4. method according to claim 3, wherein, the chlorine-containing components are organic chloride.
5. according to the method described in claim 1, wherein, the beds temperature in step (1)
Spend for 120-300 DEG C, reaction pressure is 1.0-3.0MPa, volume space velocity is 1-100h during feeding liquid-1,
Hydrogen to oil volume ratio is 1-20.
6. according to the method described in claim 1, wherein, hydrogenation catalyst described in step (1)
For the catalyst containing precious metals pt and/or Pd.
7. according to the method described in claim 1, wherein, adsorbent is solid described in step (2)
Body adsorbent.
8. method according to claim 7, wherein, the adsorbent is high-temperature dechlorinating agent.
9. according to the method described in claim 1, wherein, adsorption temp is in step (2)
120-300 DEG C, adsorptive pressure is 1.0-3.0MPa.
10. according to the method described in claim 1, wherein, the pressure in step (3) is
1.0-2.0MPa。
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| CN201610052334.2A CN106995720A (en) | 2016-01-26 | 2016-01-26 | A kind of liquid phase dechlorination method of chloride alkylate oil |
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| CN201610052334.2A CN106995720A (en) | 2016-01-26 | 2016-01-26 | A kind of liquid phase dechlorination method of chloride alkylate oil |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109694735A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of hydrogenation-dechlorination method of alkylate oil |
| CN109694737A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of dechlorination method of alkylate oil |
| CN109694738A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The hydrogenation-dechlorination method of alkylate oil |
| CN109694734A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The dechlorination method of alkylate oil |
| CN109694736A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of hydrogenation-dechlorination method of ionic liquid alkylate oil |
| CN111171865A (en) * | 2020-02-06 | 2020-05-19 | 中国石油大学(北京) | Dechlorination method of waste plastic pyrolysis oil |
| CN113896609A (en) * | 2021-11-16 | 2022-01-07 | 常州新东化工发展有限公司 | Method for deeply dechlorinating benzyltoluene |
| CN114426884A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | Dechlorination method of unsaturated C4 hydrocarbon raw material |
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Cited By (15)
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|---|---|---|---|---|
| CN109694734B (en) * | 2017-10-20 | 2020-11-10 | 中国石油化工股份有限公司 | Process for dechlorination of alkylate |
| CN109694738B (en) * | 2017-10-20 | 2021-01-05 | 中国石油化工股份有限公司 | Hydrodechlorination method for alkylate |
| CN109694738A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The hydrogenation-dechlorination method of alkylate oil |
| CN109694734A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The dechlorination method of alkylate oil |
| CN109694736A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of hydrogenation-dechlorination method of ionic liquid alkylate oil |
| CN109694736B (en) * | 2017-10-20 | 2021-02-05 | 中国石油化工股份有限公司 | Hydrodechlorination method for ionic liquid alkylate |
| CN109694737A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of dechlorination method of alkylate oil |
| CN109694735B (en) * | 2017-10-20 | 2020-11-10 | 中国石油化工股份有限公司 | Hydrogenation dechlorination method for alkylate oil |
| CN109694735A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | A kind of hydrogenation-dechlorination method of alkylate oil |
| CN109694737B (en) * | 2017-10-20 | 2021-01-05 | 中国石油化工股份有限公司 | Dechlorination method of alkylate oil |
| CN111171865A (en) * | 2020-02-06 | 2020-05-19 | 中国石油大学(北京) | Dechlorination method of waste plastic pyrolysis oil |
| CN111171865B (en) * | 2020-02-06 | 2022-04-01 | 中国石油大学(北京) | Dechlorination method of waste plastic pyrolysis oil |
| CN114426884A (en) * | 2020-09-27 | 2022-05-03 | 中国石油化工股份有限公司 | Dechlorination method of unsaturated C4 hydrocarbon raw material |
| CN114426884B (en) * | 2020-09-27 | 2024-02-13 | 中国石油化工股份有限公司 | Dechlorination method of unsaturated C4 hydrocarbon raw material |
| CN113896609A (en) * | 2021-11-16 | 2022-01-07 | 常州新东化工发展有限公司 | Method for deeply dechlorinating benzyltoluene |
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Application publication date: 20170801 |