CN104830370A - Treatment method for removing impurities from raw oil - Google Patents
Treatment method for removing impurities from raw oil Download PDFInfo
- Publication number
- CN104830370A CN104830370A CN201510235723.4A CN201510235723A CN104830370A CN 104830370 A CN104830370 A CN 104830370A CN 201510235723 A CN201510235723 A CN 201510235723A CN 104830370 A CN104830370 A CN 104830370A
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- CN
- China
- Prior art keywords
- stock oil
- dechlorination
- reaction
- dechlorinating agent
- deimpurity
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Abstract
The invention provides a treatment method for removing impurities from raw oil. The treatment method comprises a method for removing impurities from raw oil by using a catalyst for hydrogenation reaction and a method for adding a dechlorinating agent for dechlorination and is characterized in that the raw oil after reaction firstly enters the front part of a dechlorination tank to further remove the impurities in the raw oil, the front part of the dechlorination tank is filled with the catalyst for hydrogenation reaction, the filling ratio of the catalyst to the dechlorinating agent is 1 to 3, then the raw oil subjected to further impurity removal enters the rear part of the dechlorination tank and undergoes dechlorination reaction in the rear part of the dechlorination tank filled with the dechlorinating agent, and then NH3,H2S and H2O are removed from the dechlorinated raw oil by a separator and a fractionating tower. The treatment method has the advantages that the S and N removal effects are greatly improved under the condition of air speed increase, and the service life of a reforming catalyst is also greatly prolonged, thus effectively reducing the processing cost of reforming; the impurity removal treatment effects are good, the improvement cost is also low and the manufacturing cost is effectively saved.
Description
Technical field
Patent of the present invention relates to a kind of method of stock oil removal of impurities process, and especially a kind of catalyst for hydrogenation is to the method for stock oil removal of impurities.
Background technology
Existing a kind of application number is that CN201110320459.6 name is called that the Chinese invention patent application of " a kind of hydroprocessing process of heavy oil product " discloses a kind of hydroprocessing process of heavy oil product, the method comprises at hydrotreating reaction conditions, heavy oil product and hydrogen are introduced in multiple hydrogenators of series connection successively, and contact with the multiple hydrogenation catalyst beds in the plurality of hydrogenator, carry out hydrotreatment.The object that the method is improved is the activity making full use of all catalyzer, increases the running period of residual hydrogenation equipment.But its shortcoming is, need to arrange multiple hydrogenation reaction treater, cost is too high, and the treatment cycle time is long, and production efficiency is not high, so this hydroprocessing process needs to improve further.
Prior art is compared, the invention has the advantages that, the front portion first reacted stock oil being entered dechlorination tank removes further to S, N impurity in stock oil, the catalyzer of hydrogenation reaction is filled with in the front portion of dechlorination tank, then the stock oil after further removal of impurities is entered dechlorination tank rear portion, and dechlorination reaction is carried out in the dechlorination tank rear portion being filled with dechlorinating agent filler, the filling ratio of catalyzer and dechlorinating agent is 1: 3, and the equation of dechlorination reaction is: MO+nHCl=MCln+H
2o, then by the stock oil after dechlorination through separator and separation column removing NH
3, H
2s, H
2o, technique.Thus under making high-speed, de-S, N effect significantly improves, and reforming catalyst also extends work-ing life greatly, significantly reduces the tooling cost of reformation; And the present invention makes subsequent reformation device amount of finish can bring up to 900,000 tons/year from 800,000 of past ton/year, also have, imurity-removal of the present invention is effective, and improvement expenses is also low, effectively saves manufacturing cost.
Summary of the invention
Technical problem to be solved by this invention be provide for above-mentioned prior art present situation a kind of dechlorination effect good, simultaneously can the impurity such as effective elimination S, N and the treatment process of the low crude oil removal of impurities of Production and application cost.
The present invention solves the problems of the technologies described above adopted technical scheme: go deimpurity treatment process in this stock oil, the catalyzer comprising hydrogenation reaction carries out the method for removal of impurities to stock oil, add the method that dechlorinating agent carries out dechlorination, it is characterized in that: the method for described dechlorination is: the front portion first reacted stock oil being entered dechlorination tank removes further to the impurity in stock oil, catalyzer and the dechlorinating agent of hydrogenation reaction is filled with in the front portion of dechlorination tank, the filling ratio of catalyzer and dechlorinating agent is 1: 3, then the stock oil after further removal of impurities is entered dechlorination tank rear portion, and dechlorination reaction is carried out in the dechlorination tank rear portion being filled with dechlorinating agent, the equation of dechlorination reaction is: MO+nHCl=MCln+H
2o, then by the stock oil after dechlorination through separator and separation column removing NH
3, H
2s, H
2o, namely complete the step of stock oil reformation process, wherein M is dechlorinating agent metal, and n is non-vanishing natural number.
As improvement, the temperature in described dechlorination tank can preferably control be: 280-320 DEG C.
As improvement, the pressure in described dechlorination tank can preferably control be: 0-3.5MPa.
As improvement, described catalyzer can be preferably: the C that aluminum oxide or silicon oxide support
0-M
0, N
i-M
0catalyst system.
As improvement, described dechlorinating agent may be selected to be the copper system dechlorinating agent that alkaline earth metal oxide and carbonate are main component.
As improvement, described catalyzer may be selected to be the method that stock oil carries out removal of impurities: stock oil is added catalyzer and hydrogen in pre-hydrogenation unit, makes to carry out hydrogenation decomposition containing S, N, O, Cl compound in stock oil, transforms and generates HCl, NH
3, H
2s, H
2o, alkene generates stable hydrocarbon through hydrogenation reaction; Arsenic, copper, catalyzed dose of lead metal compound adsorb and remove.
Improve again, in described stock oil, go the master equation reacted of deimpurity treatment process to be:
One, desulphurization reaction
RSH+H
2→RH+H
2S
RSR′+2H
2→RH+R′H+H
2S
RSSR′+3H
2→RH+R′H+2H
2S
Two, deoxygenation
RO+H
2→R+H
2O
Three, denitrification reaction
R-NH
2+H
2→RH+NH
3
Four, dehalogenation
RCl+H
2→R+HCl
Five, olefin saturation
CnH
2n+H
2→CnH
2n
+2
Above-mentioned R represents and will remove impurity element, and R ' represents element different from R, and S is sulphur, and H is hydrogen, and n is expressed as non-vanishing natural number.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Deimpurity treatment process is gone in the stock oil of the embodiment of the present invention, the catalyzer comprising hydrogenation reaction to stock oil carry out removal of impurities method, add the method that dechlorinating agent carries out dechlorination, the method of described dechlorination is: the front portion first reacted stock oil being entered dechlorination tank removes further to the impurity in stock oil, is filled with the catalyzer of hydrogenation reaction in the front portion of dechlorination tank.The filling ratio of catalyzer and dechlorinating agent is 1: 3, then the stock oil after further removal of impurities is entered dechlorination tank rear portion, and carries out dechlorination reaction in the dechlorination tank rear portion being filled with dechlorinating agent, and the equation of dechlorination reaction is: MO+nHCl=MCln+H
2o, then by the stock oil after dechlorination through separator and separation column removing NH
3, H
2s, H
2o, namely completes the step of stock oil removal of impurities process, and wherein M is dechlorinating agent metal, and n is non-vanishing natural number.Temperature in dechlorination tank controls: 280-320 DEG C.Pressure-controlling in dechlorination tank is: 0-3.5MPa.Above-mentioned catalyzer is C that aluminum oxide or silicon oxide support
0-M
0, Ni-M
0catalyst system.The copper system dechlorinating agent of dechlorinating agent to be alkaline earth metal oxide and carbonate be main component.Described catalyzer to the method that stock oil carries out removal of impurities is: stock oil is added catalyzer and hydrogen in pre-hydrogenation unit, makes to carry out hydrogenation decomposition containing S, N, O, Cl compound in stock oil, transforms and generates HCl, NH
3, H
2s, H
2o, alkene generates stable hydrocarbon through hydrogenation reaction; Arsenic, copper, catalyzed dose of lead metal compound adsorb and remove.The master equation reacted of deimpurity treatment process is gone to be in stock oil:
One, desulphurization reaction
RSH+H
2→RH+H
2S
RSR′+2H
2→RH+R′H+H
2S
RSSR′+3H
2→RH+R′H+2H
2S
Two, deoxygenation
RO+H
2→R+H
2O
Three, denitrification reaction
R-NH
2+H
2→RH+NH
3
Four, dehalogenation
RCl+H
2→R+HCl
Five, olefin saturation
CnH
2n+H
2→CnH
2n
+2
Above-mentioned R represents and will remove impurity element, and R ' represents element different from R, and S is sulphur, and H is hydrogen, and n is expressed as non-vanishing natural number.
The invention will be further described below;
In treatment process of the present invention, pre-hydrorefined effect mainly removes the impurity in reforming raw oil, produces qualified treated oil, thus meets the requirement of reforming catalyst to raw material.Its principle is under the effect of catalyzer and hydrogen, makes to carry out hydrogenation decomposition containing compounds such as S, N, O in stock oil, transforms and generates NH
3, H
2s, H
2o, then through high-pressure separator and separation column removing NH
3, H
2s, H
2o; Alkene generates stable hydrocarbon through hydrogenation reaction; Catalyzed dose of the metallic compounds such as arsenic, copper, lead adsorb and remove.
The reaction occurred mainly contains:
A) desulphurization reaction
RSH+H
2→RH+H
2S
RSR′+2H
2→RH+R′H+H
2S
RSSR′+3H
2→RH+R′H+2H
2S
B) deoxygenation
RO+H
2→R+H
2O
C) denitrification reaction
R-NH
2+H
2→RH+NH
3
D) dehalogenation
RCL+H
2→R+HCL
E) olefin saturation
CnH
2n+H
2→CnH
2n
+2
On the one hand when there being water to exist, HCl and H
2s can the very low acid attack environment of water-soluble generation pH value, namely forms galvanic corrosion, makes the matter worse especially at liquid phase position to metallic corrosion, particularly also can produce " dew point " corrosion at phase transformation position, occur pitting corrosion perforated phenomenon.Work as NH on the other hand
3when existing with HCl, can form ammonia chloride, at low-temperature section crystallization salt, sulphur and chlorion are to pipeline, equipment corrosion and form molysite, these mechanical impuritys such as salt and iron rust together blocking pipeline and equipment simultaneously.In order to eradicate the corrosion of chlorine, most effectual way adopts dechlorination process technology.Namely apply the principle of dechlorinating agent dechlorination, pass through chemical absorption method.That is: MO+nHCl-MCln+H
2o, M are dechlorination active ingredient, according to practical situation, adopt high temperature gas phase dechlorination process, after being directly connected on pre-hydrogenator by dechlorination tank, in the dechlorination of high temperature gas phase, its advantage is high at high temperature place chlorosity, and dechlorinating agent utilization ratio is high, thus reaches better dechlorination effect.
Reformer of the present invention carries out capacity expansion revamping, will be increased to 900,000 tons/year from 800,000 tons/year, the also corresponding increase of pre-hydrogenation amount of finish, this makes pre-hydrotreating reaction air speed increase, the pre-hydrotreating reaction degree of depth can be caused inadequate, and S, N remove also can be incomplete, thus reforming catalyst work-ing life can be affected, prior art is for addressing this problem, usual increase reactor, but cost is higher, and single pre-hydrogenator will be millions of, add supporting process furnace, improvement expenses is up to ten million.In order to cost-saving, the present invention loads again to the original dechlorination tank being only used for dechlorination, part dechlorinating agent is instead of with pre-hydrotreating reaction catalyzer during filling, dechlorination tank is used as reactor and dechlorination tank simultaneously, pre-hydrogenating materials is reacted further on dechlorination tank top, carry out advanced treatment to impurity such as S, N, dechlorination is carried out in bottom, thus ensures that the raw material after process meets the requirement of reforming catalyst.As long as ensure the filling ratio that dechlorinating agent is certain, dechlorination effect can be satisfied the demand completely, meets the requirement of S, N decreasing ratio simultaneously, makes amount of finish also have the space of lifting.
Dechlorination tank is regarded two parts by the present invention, upper part is used as reactor and carries out S, N and remove (being similar to pre-hydrogenator above, is supplement one of reaction) lower part is also used to dechlorination (acting on the same with the original dechlorination tank) filling scheme in dechlorination tank and is:
Claims (7)
1. go deimpurity treatment process in a stock oil, the catalyzer comprising hydrogenation reaction carries out the method for removal of impurities to stock oil, add the method that dechlorinating agent carries out dechlorination, it is characterized in that: the method for described dechlorination is: the front portion first reacted stock oil being entered dechlorination tank removes further to the impurity in stock oil, the catalyzer of hydrogenation reaction is filled with in the front portion of dechlorination tank, the filling ratio of catalyzer and dechlorinating agent is 1: 3, then the stock oil after further removal of impurities is entered dechlorination tank rear portion, and dechlorination reaction is carried out in the dechlorination tank rear portion being filled with dechlorinating agent, the equation of dechlorination reaction is: MO+nHCl=MCln+H
2o, then by the stock oil after dechlorination through separator and separation column removing NH
3, H
2s, H
2o, namely complete the step of stock oil reformation process, wherein M is dechlorinating agent metal, and n is non-vanishing natural number.
2. go deimpurity treatment process in stock oil according to claim 1, it is characterized in that: the temperature control in described dechlorination tank is: 280-320 DEG C.
3. go deimpurity treatment process in stock oil according to claim 2, it is characterized in that: the pressure-controlling in described dechlorination tank is: 0-3.5MPa.
4. go deimpurity treatment process according in described stock oil arbitrary in claims 1 to 3, it is characterized in that: described catalyzer is the C that aluminum oxide or silicon oxide support
o-M
o, N
i-M
ocatalyst system.
5. go deimpurity treatment process according in described stock oil arbitrary in claims 1 to 3, it is characterized in that: the copper system dechlorinating agent of described dechlorinating agent to be alkaline earth metal oxide and carbonate be main component.
6. go deimpurity treatment process according in described stock oil arbitrary in claims 1 to 3, it is characterized in that: described catalyzer to the method that stock oil carries out removal of impurities is: stock oil is added catalyzer and hydrogen in pre-hydrogenation unit, make to carry out hydrogenation decomposition containing S, N, O, Cl compound in stock oil, transform and generate HCl, NH
3, H
2s, H
2o, alkene generates stable hydrocarbon through hydrogenation reaction; Arsenic, copper, catalyzed dose of lead metal compound adsorb and remove.
7. go deimpurity treatment process in stock oil according to claim 6, it is characterized in that: in described stock oil, go the master equation reacted of deimpurity treatment process to be:
One, desulphurization reaction
RSH+H
2→RH+H
2S
RSR′+2H
2→RH+R′H+H
2S
RSSR′+3H
2→RH+R′H+2H
2S
Two, deoxygenation
RO+H
2→R+H
2O
Three, denitrification reaction
R-NH
2+H
2→RH+NH
3
Four, dehalogenation
RCl+H
2→R+HCl
Five, olefin saturation
CnH
2n+H
2→CnH
2n
+2
Above-mentioned R represents and will remove impurity element, and R ' represents element different from R, and S is sulphur, and H is hydrogen, and n is expressed as non-vanishing natural number.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510235723.4A CN104830370A (en) | 2015-04-30 | 2015-04-30 | Treatment method for removing impurities from raw oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510235723.4A CN104830370A (en) | 2015-04-30 | 2015-04-30 | Treatment method for removing impurities from raw oil |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104830370A true CN104830370A (en) | 2015-08-12 |
Family
ID=53808576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510235723.4A Pending CN104830370A (en) | 2015-04-30 | 2015-04-30 | Treatment method for removing impurities from raw oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104830370A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129093A (en) * | 2019-05-21 | 2019-08-16 | 山东京博石油化工有限公司 | A kind of pre-hydrotreating reaction system |
| CN113831938A (en) * | 2021-11-01 | 2021-12-24 | 海南盈科生物科技有限公司 | Dechlorination method for high-chlorine raw material hydrogenation process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101695663A (en) * | 2009-10-27 | 2010-04-21 | 长春惠工净化工业有限公司 | Hydrogenation dechlorinating refined catalyst and preparation method thereof |
| CN101705111A (en) * | 2009-11-03 | 2010-05-12 | 长春惠工净化工业有限公司 | Reformed pre-hydrogenated dechlorination process |
| CN103127903A (en) * | 2013-03-22 | 2013-06-05 | 沈阳三聚凯特催化剂有限公司 | Normal-temperature dechlorinating agent |
| CN104437342A (en) * | 2014-12-17 | 2015-03-25 | 天津工业大学 | High-chloride-capacity liquid-phase dechlorinating agent as well as preparation method and application thereof |
-
2015
- 2015-04-30 CN CN201510235723.4A patent/CN104830370A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101695663A (en) * | 2009-10-27 | 2010-04-21 | 长春惠工净化工业有限公司 | Hydrogenation dechlorinating refined catalyst and preparation method thereof |
| CN101705111A (en) * | 2009-11-03 | 2010-05-12 | 长春惠工净化工业有限公司 | Reformed pre-hydrogenated dechlorination process |
| CN103127903A (en) * | 2013-03-22 | 2013-06-05 | 沈阳三聚凯特催化剂有限公司 | Normal-temperature dechlorinating agent |
| CN104437342A (en) * | 2014-12-17 | 2015-03-25 | 天津工业大学 | High-chloride-capacity liquid-phase dechlorinating agent as well as preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110129093A (en) * | 2019-05-21 | 2019-08-16 | 山东京博石油化工有限公司 | A kind of pre-hydrotreating reaction system |
| CN113831938A (en) * | 2021-11-01 | 2021-12-24 | 海南盈科生物科技有限公司 | Dechlorination method for high-chlorine raw material hydrogenation process |
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| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150812 |
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| RJ01 | Rejection of invention patent application after publication |