CN109082295A - A kind of burnt liquid receipts of suppression increase income agent and preparation method thereof - Google Patents
A kind of burnt liquid receipts of suppression increase income agent and preparation method thereof Download PDFInfo
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- CN109082295A CN109082295A CN201811019475.XA CN201811019475A CN109082295A CN 109082295 A CN109082295 A CN 109082295A CN 201811019475 A CN201811019475 A CN 201811019475A CN 109082295 A CN109082295 A CN 109082295A
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- 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- 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
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
-
- 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
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/02—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of corrosion inhibitors
-
- 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
- C10G75/00—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general
- C10G75/04—Inhibiting corrosion or fouling in apparatus for treatment or conversion of hydrocarbon oils, in general by addition of antifouling agents
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- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Lubricants (AREA)
Abstract
The present invention relates to a kind of burnt liquid receipts of suppression to increase income agent and preparation method thereof, the suppression coke liquid receipts increase income agent and use antioxidant, antisludging agent, polymerization inhibitor, dispersing agent, corrosion inhibiter and solvent naphtha as raw material and carry out weight proportion appropriate, under the synergistic effect of above-mentioned each raw material component, the suppression coke liquid receipts being finally prepared increase income agent, under the premise of not influencing product property, process of inhibition green coke, reduce gas yield, increase liquid oil yield, and easy to operate, it is good in economic efficiency.
Description
Technical field
The invention belongs to Petroleum Refining Additives technical fields, and in particular to a kind of burnt liquid receipts of suppression increase income agent and preparation method thereof.
Background technique
Currently, 85% or more coking treatment process belongs to delayed coking type in the world.In the technical process, heavy
Oil product is heated to temperature required for pyrogenetic reaction (480-550 DEG C) through tubular heater, and is allowed to the furnace tubing that speeds away,
Oil product carries out cracking and condensation reaction in coke drum, generates the liquid product and coke product of gas products, different boiling.It should
Mature technology, low operation cost are suitble to the mink cell focus deep processing of various properties, especially suitable for largely handling slag inferior
Oil.
Delayed coker operation and the main target of design are farthest to improve liquid yield, reduce coke and produce
Amount produces the gasoline and diesel oil for being suitble to downstream unit processing.Under normal conditions, delayed coking unit liquid yield is generally 70%
Left and right, and coke value is low, therefore, Delayed Coking Technology is being studied and improved always in each major oil companies of the world, to improve liquid
Body yield reduces coke yield, and liquid yield is every to improve 1%, and huge economic benefit can be brought to refinery.Based on this,
The burnt liquor that increases of delayed coking unit application suppression has important practical significance to improve liquid yield.
The research in terms of many delayed cokings increase liquor is carried out domestic this year.Patent CN1244669C discloses one kind
Mink cell focus delayed coking cracks activating additive and preparation method thereof, proposes a kind of mink cell focus delayed coking cracking activation addition
Agent is lanthanide rare organic compound (lanthanum of aphthenic acids or fatty acid, praseodymium or cerium salt) 20-40wt% by weight its ingredient,
Matal deactivator (one of molybdenum dialkyl-dithiophosphate, antimony dialkyldithiophosphate or dialkyl dithiophosphoric acid tin)
5-15wt%, high molecular surfactant (C8-C12One of alkyl phenol polyoxyethylene ether, anhydrous sorbitol polyoxyethylene)
10-30wt%, solvent (No. 120 solvent naphthas or diesel oil or kerosene) 10-30wt% composition.However, the delay obtained of above-mentioned technology
Coking increases liquor, and the suppression coke of product increases fluidity can be general, and dosage is big when use, and at high cost, effect is poor.
Summary of the invention
In order to solve the above problems existing in the present technology, the present invention provides one kind can effectively inhibit coke yield,
The suppression coke liquid receipts for increasing lighter fluid yield increase income agent and preparation method thereof.
The technical scheme adopted by the invention is as follows:
A kind of burnt liquid receipts of suppression increase income agent, and raw material components include:
Antioxidant, 2-5 parts by weight；
Antisludging agent, 5-10 parts by weight；
Polymerization inhibitor, 5-8 parts by weight；
Dispersing agent, 10-20 parts by weight；
Corrosion inhibiter, 5-10 parts by weight；
Solvent naphtha, 47-73 parts by weight.
Further preferably it is described press down burnt liquid and receive increase income the raw material components of agent and include:
Antioxidant, 3-4 parts by weight；
Antisludging agent, 7-8 parts by weight；
Polymerization inhibitor, 6-7 parts by weight；
Dispersing agent, 12-18 parts by weight；
Corrosion inhibiter, 7-8 parts by weight；
Solvent naphtha, 55-65 parts by weight.
Further preferably it is described press down burnt liquid and receive increase income the raw material components of agent and include:
Antioxidant, 3.5 parts by weight；
Antisludging agent, 7.5 parts by weight；
Polymerization inhibitor, 6.5 parts by weight；
Dispersing agent, 15 parts by weight；
Corrosion inhibiter, 7.5 parts by weight；
Solvent naphtha, 60 parts by weight.
The antioxidant is N, N '-di-sec-butyl-p-phenyl enediamine, alkylated diphenylamine, N, and the sub- bigcatkin willow propane diamine of N '-two is pressed
According to the mixture of mass ratio 2-4:1-2:1-2 composition.
The antisludging agent is that polymaleic anhydride and lauryl amine polyoxyethylene ether are mixed according to what mass ratio 1:4-4:1 was formed
Close object.
The polymerization inhibitor is p-tert-Butylcatechol and o-tert-butyl 4, and 6- dinitrophenol is according to mass ratio 1:2-2:1
The mixture of composition.
The dispersing agent is propylene glycol block polyether.
The corrosion inhibiter is oleic acid base hydroxyethyl imidazole quinoline.
The solvent naphtha is the mixture that 12# solvent naphtha and 20# solvent naphtha are formed according to mass ratio 1:2-2:1.
The burnt liquid of the suppression receives the preparation method for increasing income agent, includes the following steps:
Antioxidant, antisludging agent, polymerization inhibitor, dispersing agent, corrosion inhibiter and solvent naphtha are taken respectively, are carried out under normal temperature and pressure conditions
Be stirred 20-30min to get.
The invention has the benefit that
The burnt liquid receipts of suppression of the present invention increase income agent, using antioxidant, antisludging agent, polymerization inhibitor, dispersing agent, corrosion inhibiter and molten
Agent oil is raw material and to carry out weight proportion appropriate, under the synergistic effect of above-mentioned each raw material component, the suppression that is finally prepared
Burnt liquid receipts increase income agent, and under the premise of not influencing product property, process of inhibition green coke reduces gas yield, increase liquid oil and receive
Rate, and it is easy to operate, it is good in economic efficiency.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, technical solution of the present invention will be carried out below
Detailed description.Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Base
Embodiment in the present invention, those of ordinary skill in the art are obtained all without making creative work
Other embodiment belongs to the range that the present invention is protected.
1g is represented in following example with 1 parts by weight.
Embodiment 1
The present embodiment provides a kind of burnt liquid receipts of suppression to increase income agent, and raw material components include:
N, N '-di-sec-butyl-p-phenyl enediamine, 2 parts by weight；
Scale inhibitor poly maleic anhydride, 10 parts by weight；
P-tert-Butylcatechol, 5 parts by weight；
Propylene glycol block polyether, 20 parts by weight；
Oleic acid base hydroxyethyl imidazole quinoline, 5 parts by weight；
20# solvent naphtha, 73 parts by weight.
Further, the present embodiment provides a kind of preparation method for pressing down burnt liquid receipts and increasing income agent, include the following steps:
Antioxidant, antisludging agent, polymerization inhibitor, dispersing agent, corrosion inhibiter and solvent naphtha are taken respectively, are carried out under normal temperature and pressure conditions
Be stirred 20min to get.
Embodiment 2
The present embodiment provides a kind of burnt liquid receipts of suppression to increase income agent, and raw material components include:
N, N '-di-sec-butyl-p-phenyl enediamine, alkylated diphenylamine, N, the sub- bigcatkin willow propane diamine of N '-two is according to mass ratio 4:2:2
The mixture of composition, 5 parts by weight；
Antisludging agent, 5 parts by weight；
P-tert-Butylcatechol, 8 parts by weight；
Propylene glycol block polyether, 10 parts by weight；
Oleic acid base hydroxyethyl imidazole quinoline, 10 parts by weight；
The mixture that 12# solvent naphtha and 20# solvent naphtha are formed according to mass ratio 2:1,47 parts by weight.
Further, the present embodiment provides a kind of preparation method for pressing down burnt liquid receipts and increasing income agent, include the following steps:
Antioxidant, antisludging agent, polymerization inhibitor, dispersing agent, corrosion inhibiter and solvent naphtha are taken respectively, are carried out under normal temperature and pressure conditions
Be stirred 30min to get.
Embodiment 3
The present embodiment provides a kind of burnt liquid receipts of suppression to increase income agent, and raw material components include:
N, N '-di-sec-butyl-p-phenyl enediamine, alkylated diphenylamine, N, the sub- bigcatkin willow propane diamine of N '-two is according to mass ratio 4:1:2
The mixture of composition, 3 parts by weight；
The mixture that scale inhibitor poly maleic anhydride and lauryl amine polyoxyethylene ether are formed according to mass ratio 1:2,8 weight
Part；
P-tert-Butylcatechol and o-tert-butyl 4, the mixture that 6- dinitrophenol is formed according to mass ratio 1:1,6 weights
Measure part；
Propylene glycol block polyether, 18 parts by weight；
Oleic acid base hydroxyethyl imidazole quinoline, 7 parts by weight；
The mixture that 12# solvent naphtha and 20# solvent naphtha are formed according to mass ratio 1:1,65 parts by weight.
Further, the present embodiment provides a kind of preparation method for pressing down burnt liquid receipts and increasing income agent, include the following steps:
Antioxidant, antisludging agent, polymerization inhibitor, dispersing agent, corrosion inhibiter and solvent naphtha are taken respectively, are carried out under normal temperature and pressure conditions
Be stirred 25min to get.
Embodiment 4
The present embodiment provides a kind of burnt liquid receipts of suppression to increase income agent, and raw material components include:
N, N '-di-sec-butyl-p-phenyl enediamine, alkylated diphenylamine, N, the sub- bigcatkin willow propane diamine of N '-two is according to mass ratio 2:2:1
The mixture of composition, 4 parts by weight；
The mixture that scale inhibitor poly maleic anhydride and lauryl amine polyoxyethylene ether are formed according to mass ratio 2:1,7 weight
Part；
P-tert-Butylcatechol and o-tert-butyl 4, the mixture that 6- dinitrophenol is formed according to mass ratio 1:1,7 weights
Measure part；
Propylene glycol block polyether, 12 parts by weight；
Oleic acid base hydroxyethyl imidazole quinoline, 8 parts by weight；
The mixture that 12# solvent naphtha and 20# solvent naphtha are formed according to mass ratio 1:1,55 parts by weight.
Further, the present embodiment provides a kind of preparation method for pressing down burnt liquid receipts and increasing income agent, include the following steps:
Antioxidant, antisludging agent, polymerization inhibitor, dispersing agent, corrosion inhibiter and solvent naphtha are taken respectively, are carried out under normal temperature and pressure conditions
Be stirred 22min to get.
Embodiment 5
The present embodiment provides a kind of burnt liquid receipts of suppression to increase income agent, and raw material components include:
N, N '-di-sec-butyl-p-phenyl enediamine, alkylated diphenylamine, N, the sub- bigcatkin willow propane diamine of N '-two is according to mass ratio 3:
The mixture of 1.5:1.5 composition, 3.5 parts by weight；
The mixture that scale inhibitor poly maleic anhydride and lauryl amine polyoxyethylene ether are formed according to mass ratio 1:1,7.5 weights
Measure part；
P-tert-Butylcatechol and o-tert-butyl 4, the mixture that 6- dinitrophenol is formed according to mass ratio 1:1,6.5
Parts by weight；
Propylene glycol block polyether, 15 parts by weight；
Oleic acid base hydroxyethyl imidazole quinoline, 7.5 parts by weight；
The mixture that 12# solvent naphtha and 20# solvent naphtha are formed according to mass ratio 1:1,60 parts by weight.
Further, the present embodiment provides a kind of preparation method for pressing down burnt liquid receipts and increasing income agent, include the following steps:
Antioxidant, antisludging agent, polymerization inhibitor, dispersing agent, corrosion inhibiter and solvent naphtha are taken respectively, are carried out under normal temperature and pressure conditions
Be stirred 25min to get.
Experimental example
1, burnt effect assessment is hindered
(1) test procedure
The burnt liquid receipts of suppression obtained by feedstock oil (decompression residuum) and embodiment 1-5 are added in autoclave and increase income agent, are protected in nitrogen
It under the conditions of shield, is stirred under certain temperature several hours, a certain amount of feedstock oil is weighed after experiment, carried out with naphtha dilute
It releases, then is filtered with filter membrane, measure the burnt content in solution.It is burnt by suppression is not added under the burnt amount and similarity condition that obtain after filtering
The feedstock oil that liquid receipts increase income agent filters resulting burnt amount (blank test) and compares, and calculates and hinders coke rate.
(2) test feedstock oil: certain refinery's decompression residuum, fundamental property are as shown in table 1.
The fundamental property of table 1- decompression residuum
| Analysis project | Certain refinery's decompression residuum |
| Density, g/m3 | 982.4 |
| Viscosity (100 DEG C), mm2/s | 614.7 |
| Carbon residue, % | 16.34 |
| Sulfur content, % | 12510 |
| Freezing point, DEG C | 37 |
| Total nitrogen, ppm | 6371 |
| Saturated hydrocarbons, % | 21.65 |
| Aromatic hydrocarbons, % | 37.96 |
| Colloid, % | 38.27 |
| Asphalitine, % | 2.12 |
Test temperature: 500 ± 5 DEG C；Test period: 6 hours or so；
Residual oil dosage: 1L or so；Medicament additional amount: 150mg/L；
(3) burnt rate calculation formula is hindered are as follows: resistance coke rate=(mIt is empty-mResistance)/mIt is empty× 100%, wherein mIt is empty、mResistanceRespectively blank test
It is measured with adding the burnt liquid receipts of suppression to increase income the burnt of agent test.
The results are shown in Table 2.
The resistance coke rate testing result of table 2- difference sample
Green coke amount, 5 gained of embodiment can be substantially reduced it can be seen from the data in Table 2 that the burnt liquid receipts of suppression are added and increase income agent
Press down burnt liquid and receive the resistance coke best performance for increasing income agent, the reduction of carbon residue value added is the most significant in oil sample after test.
2, liquid receives effect assessment
(1) test procedure
In analogue delay coking plant, the burnt liquid receipts of embodiment 1-5 gained suppression are increased income into agent respectively and are added to coking raw material
In, coking tower is entered by heating furnace and carries out cracking reaction, the product after reaction enters after fractionating column separated, generally can will
Be separated into C4Following fraction, C5- 180 DEG C of gasoline fractions, 180-350 DEG C of diesel oil distillate, 350-450 DEG C of wax oil fraction and 450
DEG C or more tail oil.The coke laydown of generation is reacted in coke drum in tower bottom, after coke is full of in coking tower, can stop into
Material, is switched to another coke drum and is similarly operated.The burnt liquid receipts of suppression are not added and increase income agent as blank control.
(2) test technology condition
Coker feed amount is 0.5-1kg/h；
Heating furnace bringing-up section outlet temperature: 480-520 DEG C, precision ± 1 DEG C is controlled；
Coke drum, fractionating column, receiving tank are respectively 0.14-1Mpa, 0.14-0.8Mpa, 0.1-0.8Mpa, control using pressure
Precision ± 5 DEG C processed；
Water injection rate: 20-100ml/h；
Test result is shown in Table 3.
Table 3- difference, which presses down burnt liquid, to be received and increases income the liquid of agent and produce effects fruit testing result
It can be seen from the data in Table 4 that the burnt liquid receipts of suppression of the present invention are added in delayed coking increases income agent, it can
The yield for significantly reducing gas and coke, to improve liquid yield.Meanwhile it being sent out after carrying out chemical composition analysis to liquid product
Now, addition presses down burnt liquid and receives the hydrocarbon system's composition for increasing income agent front and back gasoline fraction, diesel oil distillate and wax oil fraction, sulphur, nitrogen content and coagulate
The physicochemical properties such as solid point, carbon residue do not change.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of burnt liquid receipts of suppression increase income agent, which is characterized in that raw material components include:
Antioxidant, 2-5 parts by weight；
Antisludging agent, 5-10 parts by weight；
Polymerization inhibitor, 5-8 parts by weight；
Dispersing agent, 10-20 parts by weight；
Corrosion inhibiter, 5-10 parts by weight；
Solvent naphtha, 47-73 parts by weight.
2. the burnt liquid receipts of suppression according to claim 1 increase income agent, which is characterized in that raw material components include:
Antioxidant, 3-4 parts by weight；
Antisludging agent, 7-8 parts by weight；
Polymerization inhibitor, 6-7 parts by weight；
Dispersing agent, 12-18 parts by weight；
Corrosion inhibiter, 7-8 parts by weight；
Solvent naphtha, 55-65 parts by weight.
3. the burnt liquid receipts of suppression according to claim 1 increase income agent, which is characterized in that raw material components include:
Antioxidant, 3.5 parts by weight；
Antisludging agent, 7.5 parts by weight；
Polymerization inhibitor, 6.5 parts by weight；
Dispersing agent, 15 parts by weight；
Corrosion inhibiter, 7.5 parts by weight；
Solvent naphtha, 60 parts by weight.
4. the burnt liquid receipts of suppression according to claim 1 increase income agent, which is characterized in that the antioxidant is N, N '-di-sec-butyl
P-phenylenediamine, alkylated diphenylamine, N, the mixture that the sub- bigcatkin willow propane diamine of N '-two is formed according to mass ratio 2-4:1-2:1-2.
5. the burnt liquid receipts of suppression according to claim 1 increase income agent, which is characterized in that the antisludging agent is polymaleic anhydride and ten
The mixture that dialkylamine polyoxyethylene ether is formed according to mass ratio 1:4-4:1.
6. the burnt liquid receipts of suppression according to claim 1 increase income agent, which is characterized in that the polymerization inhibitor is to tert-butyl o benzene two
Phenol and o-tert-butyl 4, the mixture that 6- dinitrophenol is formed according to mass ratio 1:2-2:1.
7. the burnt liquid receipts of suppression according to claim 1 increase income agent, which is characterized in that the dispersing agent is poly- for propylene glycol block
Ether.
8. the burnt liquid receipts of suppression according to claim 1 increase income agent, which is characterized in that the corrosion inhibiter is oleic acid base ethoxy miaow
Oxazoline.
9. the burnt liquid receipts of suppression according to claim 1 increase income agent, which is characterized in that the solvent naphtha is 12# solvent naphtha and 20#
The mixture that solvent naphtha is formed according to mass ratio 1:2-2:1.
10. the described in any item preparation methods for pressing down burnt liquid receipts and increasing income agent of claim 1-9, which is characterized in that including walking as follows
It is rapid:
Antioxidant, antisludging agent, polymerization inhibitor, dispersing agent, corrosion inhibiter and solvent naphtha are taken respectively, are stirred under normal temperature and pressure conditions
Mix 20-30min to get.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111826217A (en) * | 2020-08-10 | 2020-10-27 | 广东石油化工学院 | Low-carbon light-color sulfur-free chlorine-free ash-free polymerization inhibitor and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101665287A (en) * | 2008-09-05 | 2010-03-10 | 华东电力试验研究院有限公司 | Scale inhibitor |
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| CN111826217A (en) * | 2020-08-10 | 2020-10-27 | 广东石油化工学院 | Low-carbon light-color sulfur-free chlorine-free ash-free polymerization inhibitor and application thereof |
| CN111826217B (en) * | 2020-08-10 | 2022-06-07 | 广东石油化工学院 | Low-carbon light-color sulfur-free chlorine-free ash-free polymerization inhibitor and application thereof |
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| CN109082295B (en) | 2021-05-18 |
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