CN1325609C - Liquid organic denitrifying agent without separating nitrogen slag and denitrifying method - Google Patents
Liquid organic denitrifying agent without separating nitrogen slag and denitrifying method Download PDFInfo
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- CN1325609C CN1325609C CNB2004100964268A CN200410096426A CN1325609C CN 1325609 C CN1325609 C CN 1325609C CN B2004100964268 A CNB2004100964268 A CN B2004100964268A CN 200410096426 A CN200410096426 A CN 200410096426A CN 1325609 C CN1325609 C CN 1325609C
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- Prior art keywords
- acid
- organic
- denitrifier
- liquid organic
- heavy distillate
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- 239000007788 liquid Substances 0.000 title claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 36
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 16
- 239000002893 slag Substances 0.000 title claims description 9
- 239000003795 chemical substances by application Substances 0.000 title description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 21
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 13
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims abstract description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 6
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000019260 propionic acid Nutrition 0.000 claims abstract description 5
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims abstract description 5
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 150000002894 organic compounds Chemical class 0.000 claims description 8
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 150000001298 alcohols Chemical class 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- -1 oxygen organic acid Chemical class 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 4
- KKHUSADXXDNRPW-UHFFFAOYSA-N malonic anhydride Chemical compound O=C1CC(=O)O1 KKHUSADXXDNRPW-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 abstract 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 21
- 150000002830 nitrogen compounds Chemical class 0.000 description 21
- 239000003921 oil Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 238000004523 catalytic cracking Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A liquid organic denitrifier for heavy fractional oil is prepared from organic acid (50-80%) and alcohol (20-50%), which is one or two of acetic acid, propionic acid, ethanedioic acid and propanedioic acid, and alcohol (one or two of methanol, alcohol, ethanediol, propanediol, isopropanol and n-propanol through pumping at 30-100 deg.C to heavy fractional oil to generate complex which is mutually soluble with heavy fractional oil.
Description
Technical field
The present invention relates to the heavy distillate dealkalize nitrogen method in the petroleum refining industry, be that a kind of liquid organic complex denitrfying agent of employing shields the basic nitrogen compound in the heavy distillate specifically, reduce the toxic action of basic nitrogen compound, improved light oil yield cracking catalyst.Be mainly used in catalytic cracking unit.
Technical background
Catalytic cracking is a processing mode most effective in the oil secondary processing, so refinery enlarges its raw material sources as possible.Heavy distillate is its main raw material, but heavy distillate basic nitrogen compound content height, basic nitrogen compound can make cracking catalyst poison, thereby loses activity, and the result descends light oil yield, and coke yield rises.Document shows heavily urges the stock oil basic nitrogen compound less than 0.1% o'clock, when the every increase by 0.01% of basic nitrogen compound (m), and light oil yield decline 2～3% (m).In order to overcome this problem of heavy distillate work in-process, taked many technical measures, effect is all undesirable.The present invention's employing adds a kind of nitrogen slag in heavy distillate do not need isolating liquid organic denitrifier and denitrogenation method, and the complexing nitride and the heavy distillate of generation dissolve each other, and need not separate.Has high economic benefit.
Denitride technology mainly concentrates on lubricating oil and lubricant base aspect both at home and abroad at present.For example the denitrfying agent described in CN1103106A, CN1045459A, CN1176289A and the CN1177626A all needs treated oil to separate with the nitrogen slag.Heavy distillate is very big in difficulty aspect the separation for handling.U.S. Pat 4329222, US3223618 and US4071435 adopt the metal halide denitrification effect better, but metal halide is poisonous, produces the expense height, are unfavorable for the industry popularization.Domestic employing nitrogen slag does not need the application of isolating denitrfying agent aspect heavy distillate to yet there are no any report.As in industrial application, all do not appear in the newspapers both at home and abroad.
Summary of the invention
The purpose of this invention provides a kind of nitrogen slag and does not need isolating liquid organic denitrifier and denitrogenation method, adopts a kind of simple method to remove basic nitrogen compound in the heavy distillate, to improve the quality of heavy distillate, is convenient to following process.This method is a kind of liquid organic denitrifier that adds our invention in heavy distillate, make the basic nitrogen compound in it and the heavy distillate form neutral complex, can reduce the basic nitrogen compound in the heavy distillate more than 50%, thereby reduce the influence of alkali nitrogen in catalysis processing.
A kind of liquid organic denitrifier that from heavy distillate, removes basic nitrogen compound, be particularly useful for boiling point at the wax tailings more than 300 ℃, mixed gatch, catalytic cracking mixing raw material and vacuum residuum, liquid organic denitrifier by two or more contain the oxygen organic acid and alcohols is formed, be liquid in 30～100 ℃ of temperature ranges, can use pump delivery, denitrfying agent comprises organic acid, alcohols, wherein organic acid 50%～80%, alcohols 20%～50%, said organic acid is an acetic acid, propionic acid, oxalic acid, one or both organic compound in the propanedioic acid, alcohols is a methyl alcohol, ethanol, ethylene glycol, propylene glycol, Virahol, one or both organic compound in the n-propyl alcohol.
Add acid anhydrides in organic acid, acid anhydrides is one or both organic compound in oxalic acid acid anhydride, malonic anhydride and the acetic anhydride, to increase its acidity.
Acetic acid 30～60%, propionic acid 10～20%, two or more oxygen-containing organic compound in oxalic acid 40～80%, propanedioic acid 20～50%, oxalic acid acid anhydride 20～30%, malonic anhydride 30～50%, acetic anhydride 30～60%, methyl alcohol 10～50%, ethanol 5～30%, ethylene glycol 10～30%, propylene glycol 5～20%, Virahol 20～80%, the n-propyl alcohol 10～30%.
The step of denitrogenation method is: above-mentioned liquid organic denitrifier is poured into 0.05%～2.0% ratio in the container of heavy distillate, be heated to 50 ℃～150 ℃ gradually when evenly stirring, keep temperature of reaction 20～60min.
Consisting of of liquid organic denitrifier: a kind of meltage to other compounds in these compounds is more than 3 times of own wt, and formed liquid organic denitrifier density is bigger than water, greatly about 1.0～1.5g/cm
3, volatility is less than 0.1kg/hm
2The liquid organic denitrifier is a liquid state at 30～100 ℃, can directly be sent in the line of pipes of heavy distillate with pump.
Thisly can be used for the liquid organic denitrifier of heavy distillate purified, it can remove the basic nitrogen compound in the heavy distillate, can reduce the basic nitrogen compound in the heavy distillate more than 50%.The foundation that removes is that hydrogen proton and the lone-pair electron on the heavy distillate neutral and alkali nitride in the liquid organic denitrifier form complex compound, thereby avoided the strong adsorption of basic nitrogen compound on the catalytic cracking catalyst active centre, improved activity of such catalysts, deepen catalytic cracking reaction, improved the yield of light oil.Denitrfying agent should be able to be dissolved in the heavy distillate fully.
The present invention is that a kind of simple method of employing is removed the basic nitrogen compound in the heavy distillate, to improve the quality of heavy distillate, is convenient to following process.This method is a kind of liquid organic denitrifier that adds our invention in heavy distillate, make the basic nitrogen compound in it and the heavy distillate form neutral complex, can reduce the basic nitrogen compound in the heavy distillate more than 50%, thereby reduce the influence of alkali nitrogen in catalysis processing.This method is mainly used in catalytic cracking unit, and liquid denitrfying agent can directly be sent in the heavy distillate with pump in the time of 30～100 ℃, and the complex compound and the heavy distillate of generation dissolve each other, and need not separate.
Liquid organic denitrifier has lower volatility under working conditions, refining equipment is not caused corrosion, can dissolve fully with heavy distillate, and the neutral complex that it and basic nitrogen in oils thing form at the end is decomposed into CO fully at catalytic cracking reaction
2, N
2, NO
2Etc. harmless organic compound, can not pollute to environment.Liquid organic denitrifier raw material is easy to get, and is nontoxic, is convenient to industrial promotion and application.
Embodiment
Embodiment 1
Oxalic acid 80% and ethanol 20% are made into organic denitrifier, getting the grand celebration wax tailings is raw material, and the consumption of organic denitrifier is 0.4%, stirs 60min at 60 ℃, the basic nitrogen compound content of wax tailings drops to 283.2ppm by 1322.6ppm, and the alkali conversion rate of nitrogen is 78.6%.
Embodiment 2
Acetic acid 40%, methyl alcohol 40% and acetic anhydride 20% are made into organic denitrifier, getting grand celebration, heavily to urge stock oil be raw material, the consumption of organic denitrifier is 0.8%, stir 30min at 90 ℃, heavily urge the basic nitrogen compound content of stock oil to drop to 483.2ppm by 1005.3ppm, the alkali conversion rate of nitrogen is 51.9%.
Embodiment 3
Propanedioic acid 50%, ethylene glycol 45% and malonic anhydride 5% are made into organic denitrifier, getting grand celebration vacuum residuum is raw material, the consumption of organic denitrifier is 1.0%, stir 45min at 80 ℃, the basic nitrogen compound content of vacuum residuum drops to 996.2ppm by 2829.0ppm, and the alkali conversion rate of nitrogen is 64.8%.
Embodiment 4
Propionic acid 15%, Virahol 80% and oxalic acid acid anhydride 5% are made into organic denitrifier, getting the grand celebration wax tailings is raw material, the consumption of organic denitrifier is 1.4%, stir 45min at 100 ℃, the basic nitrogen compound content of wax tailings drops to 346.8ppm by 1322.6ppm, and the alkali conversion rate of nitrogen is 73.6%.
Embodiment 5
Propanedioic acid 50%, n-propyl alcohol 30% and propylene glycol 20% are made into organic denitrifier, getting the Daqing Mixing wax oil is raw material, the consumption of organic denitrifier is 1.6%, stir 60min at 120 ℃, the basic nitrogen compound content of mixed gatch drops to 203.8ppm by 786.5ppm, and the alkali conversion rate of nitrogen is 74.1%.
Claims (3)
1. a nitrogen slag does not need isolating liquid organic denitrifier, it is characterized in that: liquid organic denitrifier by two or more contain the oxygen organic acid and alcohols is formed, wherein organic acid 50%～80%, alcohols 20%～50%, said organic acid is one or both organic compound in acetic acid, propionic acid, oxalic acid, the propanedioic acid, and alcohols is one or both organic compound in methyl alcohol, ethanol, ethylene glycol, propylene glycol, Virahol, the n-propyl alcohol.
2. a kind of nitrogen slag according to claim 1 does not need isolating liquid organic denitrifier, it is characterized in that: add acid anhydrides in organic acid, acid anhydrides is one or both organic compound in oxalic acid acid anhydride, malonic anhydride and the acetic anhydride, to increase its acidity.
3. a nitrogen slag does not need the organic denitrogenation method of isolating liquid state, it is characterized in that: the step of method is: pour into claim 1 or 2 described liquid organic denitrifiers in the container of heavy distillate with 0.05%～2.0% ratio, be heated to 50 ℃～150 ℃ gradually when evenly stirring, keep temperature of reaction 20～60min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100964268A CN1325609C (en) | 2004-12-01 | 2004-12-01 | Liquid organic denitrifying agent without separating nitrogen slag and denitrifying method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100964268A CN1325609C (en) | 2004-12-01 | 2004-12-01 | Liquid organic denitrifying agent without separating nitrogen slag and denitrifying method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1782025A CN1782025A (en) | 2006-06-07 |
| CN1325609C true CN1325609C (en) | 2007-07-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100964268A Expired - Fee Related CN1325609C (en) | 2004-12-01 | 2004-12-01 | Liquid organic denitrifying agent without separating nitrogen slag and denitrifying method |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102021014A (en) * | 2009-09-15 | 2011-04-20 | 中国石油天然气股份有限公司 | Method for removing alkali nitrogen from inferior diesel oil |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4272361A (en) * | 1979-06-27 | 1981-06-09 | Occidental Research Corporation | Method for reducing the nitrogen content of shale oil |
| US4390416A (en) * | 1981-12-07 | 1983-06-28 | W. R. Grace & Co. | Catalytic cracking of hydrocarbons |
| US4483763A (en) * | 1982-12-27 | 1984-11-20 | Gulf Research & Development Company | Removal of nitrogen from a synthetic hydrocarbon oil |
| US4743360A (en) * | 1985-10-24 | 1988-05-10 | Labofina, S.A. | Process for removing basic nitrogen compounds from gas oils |
| US4790930A (en) * | 1987-05-29 | 1988-12-13 | Shell Oil Company | Two-step heterocyclic nitrogen extraction from petroleum oils |
-
2004
- 2004-12-01 CN CNB2004100964268A patent/CN1325609C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4272361A (en) * | 1979-06-27 | 1981-06-09 | Occidental Research Corporation | Method for reducing the nitrogen content of shale oil |
| US4390416A (en) * | 1981-12-07 | 1983-06-28 | W. R. Grace & Co. | Catalytic cracking of hydrocarbons |
| US4483763A (en) * | 1982-12-27 | 1984-11-20 | Gulf Research & Development Company | Removal of nitrogen from a synthetic hydrocarbon oil |
| US4743360A (en) * | 1985-10-24 | 1988-05-10 | Labofina, S.A. | Process for removing basic nitrogen compounds from gas oils |
| US4790930A (en) * | 1987-05-29 | 1988-12-13 | Shell Oil Company | Two-step heterocyclic nitrogen extraction from petroleum oils |
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| Publication number | Publication date |
|---|---|
| CN1782025A (en) | 2006-06-07 |
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Granted publication date: 20070711 |