CN1309810C - Coke inhibitor of high-temperature refining equipment - Google Patents
Coke inhibitor of high-temperature refining equipment Download PDFInfo
- Publication number
- CN1309810C CN1309810C CNB2005100429910A CN200510042991A CN1309810C CN 1309810 C CN1309810 C CN 1309810C CN B2005100429910 A CNB2005100429910 A CN B2005100429910A CN 200510042991 A CN200510042991 A CN 200510042991A CN 1309810 C CN1309810 C CN 1309810C
- Authority
- CN
- China
- Prior art keywords
- alkyl
- inhibitor
- oil
- thiophosphatephosphorothioate
- butyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a coke inhibitor of a high-temperature petroleum refining device. The coke inhibitor is prepared from 75 to 98 wt% of thiophosphoric acid alkyl benzene monosulfonic acid bisamine salt, 1 to 15 wt% of antioxidant and 1 to 10 wt% of polymerization inhibitor as raw materials and organic solvent accounting for 20% of the total weight of the three ingredients, wherein the antioxidant is hydroquinone or 4, 4-methylenebis (2, 6-di-tert-butyl phenol) or 2, 6-di-tert-butyl hydroxytoluene or N, N'-di-secondary-ursol or phenyl-alpha naphthylamine; the polymerization inhibitor is benzoquinone or p-tert-butyl catechol; the organic solvent is xylene or diesel oil or kerosene or solvent oil. The present invention has the advantages of good coke inhibiting effect, high stability, wide applicable temperature range, easy production technology, etc., and is suitable for inhibiting the coke formation of the high-temperature devices of crude oil distillation, catalytic cracking, viscosity breaking, delayed coking, ethene preparation by cracking, etc., especially for inhibiting the coke formation and the scale deposition of high-temperature services, such as delayed coking heating furnaces, catalytic cracking settling devices, large oil device pipelines, ethene cracking furnaces, etc.
Description
Technical field
The invention belongs under the situation that does not have hydrogen, the thermal non-catalytic cracking technical field of hydrocarbon ils is specifically related to prevent or remove incrustation.
Technical background
Along with the continuous intensification of oil heaviness trend, the raw material that is used for the refining of petroleum and the petrochemical complex course of processing becomes gradually and heavily becomes bad.The stock oil change heavily becomes bad and brings very big difficulty to refining of petroleum and petrochemical complex processing, as catalytic cracking, residual hydrocracking, hydrocracking, crude distillation, delayed coking, some equipment of device such as viscosity breaking and cracking ethylene preparation, especially relevant device in the pyroprocess such as coking heater pipe, the catalytic cracking main oil gas piping, ethane cracking furnaces etc. very easily form burnt dirt, coking and fouling reduces thermal efficiency of heating furnace, the interchanger heat exchange efficiency descends, pipeline stops up, the pyrolyzer life cycle shortens, had a strong impact on the ordinary production of full scale plant, the energy consumption and the maintenance cost of device have been increased, shortened on-stream time, the economic benefit of device is not in full use.
At present, solve the burnt dirty method of refining equipment and mainly contain two kinds.A kind of is adopting process and device, method, and main passing through increases utility appliance, improves technical process and operational condition, and approach such as control stock oil character index realize.Another kind is a chemical process, and employing adds a certain amount of chemical assistant and suppresses, delays the formation of burnt dirt in equipment surface in stock oil usually.A kind of method in back have do not change technical process, do not influence normal running, filling is convenient, flexibly, advantage such as fund input is few, return period is short, make it become economy, solve the method for equipment coking and fouling problem effectively.At present, domestic and international coking equipment at lesser temps, as the catalytically cracked oil system, hydrotreatment, the hydrocracking raw material interchanger, a large amount of research report and patent have appearred, many refinerys have all been obtained a large amount of successful experiences in the use of Scale inhibitors, and to the inhibition of high temperature service coking, as the catalytic cracking main oil gas piping, settling vessel, viscosity breaking, delayed coking, the process furnace of cracking ethylene preparation etc., pyrolyzer, domestic also mainly is to start with from improving processing condition and increasing utility appliance, abroad since last century the fifties just the research in this field, a considerable amount of anticoking agent patents have appearred, domestic in recent years a few thing that this has also been launched, but because coking position temperature height, general Scale inhibitors all can lose efficacy because of decomposition, so the coking of high temperature position is puzzlement refiner and investigator's a difficult problem always.
The research that is used for the anticoking agent of refining of petroleum and petrochemical complex pyroprocess relevant device starts from nineteen fifties, still has many companies to be devoted to the exploitation in this field so far in the world.Facts have proved and use anticoking agent to have vital role for the formation that prevents, delays and eliminate the burnt dirt of high temperature service in the refining of petroleum and the petrochemical complex course of processing.Many additives are used to suppress, alleviate the coking and fouling of high temperature service, and phosphide has the metal surface modification effect, deposit in equipment surface thereby suppress burnt dirt.U.S. Pat P4105540 discloses use list or dialkyl group, aryl, aralkyl, cycloalkyl, thiazolinyl phosphoric acid ester as anticoking agent.U.S. Pat P4105540 discloses use trialkyl, aryl, aralkyl, cycloalkyl, thiazolinyl phosphoric acid ester as anticoking agent.U.S. Pat P4105540] use trialkyl, aryl, aralkyl, cycloalkyl, alkenyl substituted phosphoric acid ester are disclosed as anticoking agent.U.S. Pat P5460712 discloses use trimerization or poly aryl phosphate ester as anticoking agent.U.S. Pat P4024048,4024049,4024050,4024051 discloses use list or diphosphate or phosphoric acid ester as anticoking agent.
Sulfide also has the metal surface modification effect, and U.S. Pat P4116812 discloses use sulfide such as dimethylsulphide, dimethyl disulphide, mercaptan or polysulphide as metal surface modifier, with the coking of ethene suppressing pyrolyzer.U.S. Pat P5093032 discloses the mixture of use boride and dihydroxy-benzene as anticoking agent, and boride is as metal surface modifier, and dihydroxy-benzene is as free radical terminator.USP5093032 discloses the coking of using the boric acid ammonium salt to reach equipment surface more than 800 ℃ with the inhibition temperature as metal surface modifier.
From above-mentioned patent as can be seen the inhibition of pyroprocess relevant devices coking mainly be from metal surface modification and stop radical chain reaction and start with, what metal surface modifier was commonly used is boride, organic sulfide, phosphoric acid ester or phosphoric acid salt, wherein the phosphoric acid ester effect is the most obvious, but phosphoric acid ester causes corrosion after decomposing easily, and the derivative of phosphate amine salt does not also occur in patent in the past as anticoking agent.
Summary of the invention
Technical problem to be solved by this invention is to overcome the shortcoming of above-mentioned anticoking agent, and a kind of burnt effective, good stability, the Applicable temperature scope is wide, production technique is easy coke inhibitor of high-temperature refining equipment of hindering is provided.
It is to make composition by following weight percentages to solve the problems of the technologies described above the technical scheme that adopted:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 75～98%
Oxidation inhibitor 1～15%
Stopper 1～10%
Consumption of organic solvent is 20% of above-mentioned three kinds of component gross weights.
The molecular structural formula of above-mentioned thiophosphatephosphorothioate benzene sulfonamide acid diamine salt is as follows:
A is the O atom in the structural formula (1), R
1Be H or C
1～C
12Alkyl, be preferably C
2～C
8, R
2Be C
1～C
12Alkyl, be preferably C
2～C
8, R
3Be C
2～C
10Alkyl, be preferably C
2～C
6, R
4Be C
12Alkyl.
Above-mentioned oxidation inhibitor is Resorcinol or 4,4-methylene-bis (2, the 6-di-tert-butylphenol) or 2,6 ditertiary butyl p cresol or N, N '-di-sec-butyl-p-phenyl enediamine or phenyl-αNai An, N preferably, N '-di-sec-butyl-p-phenyl enediamine.Above-mentioned stopper is benzoquinones or p-ten.-butylcatechol, preferably p-ten.-butylcatechol.Above-mentioned organic solvent is dimethylbenzene or diesel oil or kerosene solvent oil, preferably solvent oil.
Preparation method's step of thiophosphatephosphorothioate benzene sulfonamide acid diamine salt is as follows:
1, adding earlier weight ratio in the flask that agitator, thermometer, dropping funnel are housed is 1: 1 solvent xylene and thiophosphoric anhydride, start agitator, behind the heat temperature raising to 60 ℃, begin to drip alkyl alcohol, the mol ratio of alkyl alcohol and thiophosphoric anhydride is 4: 1, be warming up to 80 ℃～110 ℃, reacted 3～4 hours.The sulfo-phosphide compounds of generating structure formula (2).
Till no gas is emitted the back.The cooling reaction product is to room temperature, and is standby after filtering.
A in the structural formula (2) is the O atom, R
1Be H or alkyl, R
2Be alkyl.
2, be to take by weighing alkyl benzene sulphonate (ABS), diamines at 1: 1 in molar ratio, be incorporated with in the flask of agitator, thermometer and start agitator, reacted 30～40 minutes, obtain structural formula (3) reaction product.It is standby to treat that temperature is chilled to room temperature.
3, be to take by weighing the reaction product of step 1 and step 2 at 1: 1 in molar ratio, reacted at normal temperatures 40～50 minutes that the question response product is chilled to room temperature, filter, boil off solvent, thiophosphatephosphorothioate benzene sulfonamide acid diamine salt.
Preparation method of the present invention is as follows:
With thiophosphatephosphorothioate benzene sulfonamide acid diamine salt, oxidation inhibitor, stopper and organic solvent by weight percentage example be blended in the flask, be heated to 60～70 ℃, stirred 30～60 minutes, obtain oil refinery's anti-coking agent for high-temperature equipment.
Preferred weight per distribution ratio of the present invention is:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 82～93%
Oxidation inhibitor 4～10%
Stopper 3～8%
Consumption of organic solvent is 20% of above-mentioned three kinds of component gross weights.
Optimum weight per distribution ratio of the present invention is:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 89%
Oxidation inhibitor 6%
Stopper 5%
Consumption of organic solvent is 20% of above-mentioned three kinds of component gross weights.
The present invention has not only overcome the corrodibility after general phosphoric acid ester is decomposed, and again because of having the benzene sulfonamide acid groups, make it have the function of peace and quiet, dispersion and passivating metallic surfaces simultaneously, hindering burnt effect improves greatly, stable performance, the Applicable temperature scope is wide, applicable to comparatively harsh working condition such as temperature, pressure, starting material are easy to get, and produce simple and easy to do.The present invention estimates through the laboratory, and the effect of the present invention and tritolyl phosphate, polyalkenyl thiophosphoric acid amine salt anticoking agent is greatly improved, and when filling rate was 100 μ g/g, hindering burnt rate can reach more than 85%.The present invention has advantages such as resistance Jiao is effective, good stability, the Applicable temperature scope is wide, production technique is easy.Be applicable to the coking of device high temperature services such as crude distillation, catalytic cracking, viscosity breaking, delayed coking, cracking ethylene preparation, be particularly useful for suppressing the coking and fouling of high temperature equipment such as delay coking heating furnace, catalytic cracking subsider, big oily pipeline, ethane cracking furnace.
Embodiment
The invention will be further described below in conjunction with embodiment, but these embodiment are not limitation of the present invention.
Embodiment 1
With preparation 120g product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 89g
N, N '-di-sec-butyl-p-phenyl enediamine 6g
P-ten.-butylcatechol 5g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be H, R
2Be the alkyl of C8, R
3Be C
6Alkyl, R
4Be C
12Alkyl.
Its preparation method is as follows:
With thiophosphatephosphorothioate benzene sulfonamide acid diamine salt, N, N '-di-sec-butyl-p-phenyl enediamine, p-ten.-butylcatechol and solvent oil is arranged by weight in beaker, mixing, be heated to 60～70 ℃, stirred 30～60 minutes, obtain coke inhibitor of high-temperature refining equipment.
Embodiment 2
With preparation 120g product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 75g
N, N '-di-sec-butyl-p-phenyl enediamine 15g
P-ten.-butylcatechol 10g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be C
1Alkyl, R
2Be C
1Alkyl, R
3Be C
2Alkyl, R
4Be C
12Alkyl.
Its preparation method is identical with embodiment 1.
Embodiment 3
With preparation 120g product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 98g
N, N '-di-sec-butyl-p-phenyl enediamine 1g
P-ten.-butylcatechol 1g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be C
12Alkyl, R
2Be C
12Alkyl, R
3Be the alkyl of C10, R
4Alkyl for C12.
Its preparation method is identical with embodiment 1.
Embodiment 4
With preparation 120g product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 80g
N, N '-di-sec-butyl-p-phenyl enediamine 12g
P-ten.-butylcatechol 8g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be H, R
2Be C
12Alkyl, R
3Be C
2Alkyl, R
4Be C
12Alkyl.
Its preparation method is identical with embodiment 1.
Embodiment 5
With preparation 120g product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 85g
N, N '-di-sec-butyl-p-phenyl enediamine 8g
P-ten.-butylcatechol 7g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be H, R
2Be C
1Alkyl, R
3Be C
2Alkyl, R
4Be C
12Alkyl.
Its preparation method is identical with embodiment 1.
Embodiment 6
With preparation 120g product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 85g
N, N '-di-sec-butyl-p-phenyl enediamine 8g
P-ten.-butylcatechol 7g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be H, R
2Be C
1Alkyl, R
3Be C
19Alkyl, R
4Be C
2Alkyl.
Its preparation method is identical with embodiment 1.
Embodiment 7
With preparation 120g product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 85g
N, N '-di-sec-butyl-p-phenyl enediamine 8g
P-ten.-butylcatechol 7g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be H, R
2Be C
12Alkyl, R
3Be C
10Alkyl, R
4Be C
12Alkyl.
Its preparation method is identical with embodiment 1.
Embodiment 8
With preparation 120gk product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 90g
N, N '-di-sec-butyl-p-phenyl enediamine 7g
P-ten.-butylcatechol 3g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be C
1Alkyl, R
2Be C
12Alkyl, R
3Be C
2Alkyl, R
4Be C
12Alkyl.
Its preparation method is identical with embodiment 1.
Embodiment 9
With preparation 120g product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 90g
N, N '-di-sec-butyl-p-phenyl enediamine 3g
P-ten.-butylcatechol 7g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be C
1Alkyl, R
2Be C
12Alkyl, R
3Be C
10Alkyl, R
1Be C
12Alkyl.
Its preparation method is identical with embodiment 1.
Embodiment 10
With preparation 120g product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 88g
N, N '-di-sec-butyl-p-phenyl enediamine 6g
P-ten.-butylcatechol 6g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be C
12Alkyl, R
2Be C
1Alkyl, R
3Be C
2Alkyl, R
4Be C
12Alkyl.
Its preparation method is identical with embodiment 1.
Embodiment 11
With preparation 120g product of the present invention is example, and used raw material and proportioning thereof are as follows:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 82g
N, N '-di-sec-butyl-p-phenyl enediamine 8g
P-ten.-butylcatechol 10g
Solvent oil 20g
A in the structural formula (1) is the O atom, R
1Be C
12Alkyl, R
2Be C
1Alkyl, R
10Be C
3Alkyl, R
4Be C
12Alkyl.
Its preparation method is identical with embodiment 1.
Embodiment 12
N among the above embodiment 1～11, N '-di-sec-butyl-p-phenyl enediamine replaces with phenyl-αNai An, consumption and N, N '-di-sec-butyl-p-phenyl enediamine is identical, and solvent oil is replaced with kerosene, and consumption is identical with solvent oil.
A in the structural formula (1) is the O atom, R
1Value, R
2Value, R
3Value, R
4Value identical with respective embodiments.
Its preparation method is identical with embodiment 1.
Embodiment 13
P-ten.-butylcatechol among the above embodiment 1～11 is replaced with benzoquinones, and consumption is identical with p-ten.-butylcatechol, and solvent oil is replaced with diesel oil, and consumption is identical with solvent oil.
A in the structural formula (1) is the O atom, R
1Value, R
2Value, R
3Value, R
4Value identical with respective embodiments.
Its preparation method is identical with embodiment 1.
Embodiment 14
N among the above embodiment 1～11, N '-di-sec-butyl-p-phenyl enediamine replaces with 2,6 ditertiary butyl p cresol, consumption and N, N '-di-sec-butyl-p-phenyl enediamine is identical, and solvent oil is replaced with dimethylbenzene, and consumption is identical with solvent oil.
A in the structural formula (1) is the O atom, R
1Value, R
2Value, R
3Value, R
4Value identical with respective embodiments.
Its preparation method is identical with embodiment 1.
Embodiment 15
N among the above embodiment 1～11, N '-di-sec-butyl-p-phenyl enediamine are with 4, and 4-methylene-bis (2, the 6-di-tert-butylphenol) is replaced, consumption and N, and N '-di-sec-butyl-p-phenyl enediamine is identical, and solvent oil is replaced with kerosene, and consumption is identical with solvent oil.
A in the structural formula (1) is the O atom, R
1Value, R
2Value, R
3Value, R
4Value identical with respective embodiments.
Its preparation method is identical with embodiment 1.
Embodiment 16
N among the above embodiment 1～11, N '-di-sec-butyl-p-phenyl enediamine replaces with Resorcinol, consumption and N, N '-di-sec-butyl-p-phenyl enediamine is identical, and p-ten.-butylcatechol is replaced with benzoquinones, and consumption is identical with p-ten.-butylcatechol, solvent oil is replaced with diesel oil, and consumption is identical with solvent oil.
A in the structural formula (1) is the O atom, R
1Value, R
2Value, R
3Value, R
4Value identical with respective embodiments.
Its preparation method is identical with embodiment 1.
In order to verify beneficial effect of the present invention, the contriver adopts coke inhibitor of high-temperature refining equipment and tritolyl phosphate, the polyalkenyl thiophosphoric acid barium salt of the weight proportion preparation of the embodiment of the invention 1 (being anticoking agent 1 of the present invention during experiment) and embodiment 3 (being anticoking agent 2 of the present invention during experiment) to carry out the contrast properties experimental evaluation, investigate the quality of anticoking agent according to the gain in weight behind the dirty testing tube coking and fouling of Jiao, design and made experimental installation.The experimental evaluation situation is as follows:
One, be that stock oil compares evaluation experimental with vacuum residuum
1, experiment material
Anticoking agent of the present invention is provided by the applicant;
Vacuum residuum is stock oil, is produced by the Liaoyang refinery;
Tritolyl phosphate is produced by Peng Pu chemical plant, Shanghai;
Polyalkenyl thiophosphoric acid barium salt is by Lanzhou Oil Refinery production.
2, experimental installation
Self-control.
3, experimental technique
With pump stock oil is extracted out from head tank and to be sent into the burnt dirty testing tube that there is process furnace heating the outside, the control furnace temp is constant, and the stock oil temperature in is 150 ℃, 700 ℃ of furnace temps, the material oil outlet temperature is 490 ℃ during the experiment beginning, stock oil flow velocity 350g/h.And stock oil flow velocity and testing tube ingress temperature are remained unchanged in entire test.Experimental period 20 hours when the test beginning, does not have burnt dirt in the burnt dirty testing tube, along with the carrying out of test, burnt dirt deposition on the test tube wall increases gradually, and the weight during on-test when the weight of testing tube and off-test has a weight difference Δ G, burnt dirt is many more, and weight difference Δ G is big more.Add anticoking agent, the coking of stock oil in testing tube is inhibited, and burnt amount reduces, and weight difference Δ G reduces.
Hindering burnt effect can represent with the burnt rate of resistance.
In the formula, G
0, g
0Be respectively and do not add anticoking agent, the weight of burnt dirty testing tube when on-test, end.G, g are respectively and add a certain amount of anticoking agent, the weight of burnt dirty testing tube when on-test, end.
Δ G
Empty=G
0-g
0Δ G
Agent=G-g
4, experimental result
Experimental result sees Table 1.
Table 1 is that stock oil compares evaluation experimental table as a result with vacuum residuum
| Sample | Dosage (μ g/g) | ΔG，g | Hinder burnt rate (%) |
| Blank | / | 22.62 | / |
| Anticoking agent 1 of the present invention | 50 | 6.09 | 73.07 |
| Anticoking agent 1 of the present invention | 100 | 1.87 | 91.73 |
| Anticoking agent 2 of the present invention | 50 | 6.74 | 70.2 |
| Anticoking agent 2 of the present invention | 100 | 2.62 | 88.4 |
| Tritolyl phosphate | 50 | 8.98 | 52.6 |
| Tritolyl phosphate | 100 | 13.96 | 60.3 |
| Polyalkenyl thiophosphoric acid barium salt | 50 | 8.66 | 61.7 |
| Polyalkenyl thiophosphoric acid barium salt | 100 | 6.26 | 72.3 |
Two, be that stock oil compares evaluation experimental with the petroleum naphtha
1, experiment material
Anticoking agent of the present invention is provided by the applicant;
Petroleum naphtha is a stock oil, by Luoyang refinery production;
Tritolyl phosphate is produced by Peng Pu chemical plant, Shanghai;
Polyalkenyl thiophosphoric acid barium salt is by Lanzhou Oil Refinery production.
2, experimental installation
Self-control.
3, experimental technique
Stock oil extracted out to mix with 300 ℃ of superheated vapours from head tank with pump send into the process furnace preheating section, be preheating to 650 ℃, enter the process furnace radiation section then, the material oil outlet temperature is 850 ℃ during the experiment beginning, stock oil flow velocity 350g/h.Keep the stock oil flow velocity and testing tube ingress temperature remains unchanged in entire test, experimental period 20 hours, experiment finishes the weight of incrustation testing tube in the back weighing radiation section, when the test beginning, there is not burnt dirt in the burnt dirty testing tube, along with the carrying out of test, burnt dirt deposition on the test tube wall increases gradually, weight during on-test when the weight of testing tube and off-test has a weight difference Δ G, and burnt dirt is many more, and weight difference Δ G is big more.Add anticoking agent, the coking of stock oil in testing tube is inhibited, and burnt amount reduces, and weight difference Δ G reduces.
Hindering burnt effect can represent with the burnt rate of resistance.
In the formula, G
0, g
0Be respectively and do not add anticoking agent, the weight of burnt dirty testing tube when on-test, end.
G, g are respectively and add a certain amount of anticoking agent, the weight of burnt dirty testing tube when on-test, end.
Δ G
Empty=G
0-g
0
Δ G
Agent=G-g
4, experimental result
Experimental result sees Table 2.
5, conclusion
By above result as can be seen the present invention be greatly improved than the effect of tritolyl phosphate, polyalkenyl thiophosphoric acid barium salt anticoking agent, when filling rate was 100 μ g/g, hindering burnt rate can reach more than 80%.
Table 2 is that stock oil compares evaluation experimental table as a result with the petroleum naphtha
| Sample | Dosage (μ g/g) | ΔG，g | Hinder burnt rate (%) |
| Blank | / | 28.36 | / |
| Anticoking agent 1 of the present invention | 50 | 7.99 | 71.81 |
| Anticoking agent 1 of the present invention | 100 | 3.27 | 88.45 |
| Anticoking agent 2 of the present invention | 50 | 9.55 | 66.32 |
| Anticoking agent 2 of the present invention | 100 | 5.01 | 82.35 |
| Tritolyl phosphate | 50 | 14.96 | 47.25 |
| Tritolyl phosphate | 100 | 13.28 | 53.16 |
| Polyalkenyl thiophosphoric acid barium salt | 50 | 18.64 | 34.28 |
| Polyalkenyl thiophosphoric acid barium salt | 100 | 15.53 | 45.23 |
Claims (7)
1, a kind of coke inhibitor of high-temperature refining equipment is characterized in that it is to make composition by following weight percentages:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 75～98%
Oxidation inhibitor 1～15%
Stopper 1～10%
Consumption of organic solvent is 20% of above-mentioned three kinds of component gross weights;
The molecular structural formula of above-mentioned thiophosphatephosphorothioate benzene sulfonamide acid diamine salt is as follows:
A is the O atom in the structural formula (1), R
1Be H or C
1～C
12Alkyl, R
2Be C
1～C
12Alkyl, R
3Be C
2～C
10Alkyl, R
1Be C
12Alkyl;
Above-mentioned oxidation inhibitor is Resorcinol or 4,4-methylene-bis (2, the 6-di-tert-butylphenol) or 2,6-ditertbutylparacresol or N, N '-di-sec-butyl-p-phenyl enediamine or phenyl-αNai An, above-mentioned stopper is benzoquinones or p-ten.-butylcatechol, and above-mentioned organic solvent is dimethylbenzene or diesel oil or kerosene or solvent oil.
2,, it is characterized in that wherein the weight percent proportioning of each raw material is according to the described coke inhibitor of high-temperature refining equipment of claim 1:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 82～93%
Oxidation inhibitor 4～10%
Stopper 3～8%
Consumption of organic solvent is 20% of above-mentioned three kinds of component gross weights.
3,, it is characterized in that wherein the weight percent proportioning of each raw material is according to the described coke inhibitor of high-temperature refining equipment of claim 1:
Thiophosphatephosphorothioate benzene sulfonamide acid diamine salt 89%
Oxidation inhibitor 6%
Stopper 5%
Consumption of organic solvent is 20% of above-mentioned three kinds of component gross weights.
4, according to claim 1 or 2 or 3 described coke inhibitor of high-temperature refining equipment, it is characterized in that: in the structural formula (1) of said component thiophosphatephosphorothioate benzene sulfonamide acid diamine salt, R wherein
1Be C
2～C
8Alkyl, R
2Be C
2～C
8Alkyl, R
3Be C
2～C
6Alkyl.
5, according to claim 1 or 2 or 3 described coke inhibitor of high-temperature refining equipment, it is characterized in that: wherein component oxidation inhibitor is N, N '-di-sec-butyl-p-phenyl enediamine.
6, according to claim 1 or 2 or 3 described coke inhibitor of high-temperature refining equipment, it is characterized in that: wherein the component stopper is a p-ten.-butylcatechol.
7, according to claim 1 or 2 or 3 described coke inhibitor of high-temperature refining equipment, it is characterized in that: wherein the component organic solvent is a solvent oil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100429910A CN1309810C (en) | 2005-07-26 | 2005-07-26 | Coke inhibitor of high-temperature refining equipment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100429910A CN1309810C (en) | 2005-07-26 | 2005-07-26 | Coke inhibitor of high-temperature refining equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1712494A CN1712494A (en) | 2005-12-28 |
| CN1309810C true CN1309810C (en) | 2007-04-11 |
Family
ID=35718290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100429910A Expired - Fee Related CN1309810C (en) | 2005-07-26 | 2005-07-26 | Coke inhibitor of high-temperature refining equipment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1309810C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705124B (en) * | 2009-11-27 | 2012-10-03 | 济南开发区星火科学技术研究院 | Diesel oxidized stabilizer composite |
| CN102071047A (en) * | 2011-01-27 | 2011-05-25 | 天津市瑞德赛恩新材料开发有限公司 | Residual oil modifier for coking delaying device and use thereof |
| CN102776027A (en) * | 2012-08-13 | 2012-11-14 | 关平 | Coking-prevention light oil yield increasing agent for delayed coker of oil refinery |
| CN104313266B (en) * | 2014-09-30 | 2016-05-18 | 宁波保润石化有限公司 | A kind of for preparing the method for quick bright quenc hing oil |
| CN105567298B (en) * | 2014-10-09 | 2017-08-29 | 中国石油化工股份有限公司 | Improve the method for catalytic cracking production distribution using weight carbon nine |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4842716A (en) * | 1987-08-13 | 1989-06-27 | Nalco Chemical Company | Ethylene furnace antifoulants |
| CN1218095A (en) * | 1997-11-24 | 1999-06-02 | 中国石油化工总公司 | Coking and scaling inhibitor and preparation and use thereof |
| CN1448490A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Coking-suppressing antiscale and application thereof |
| JP2007162589A (en) * | 2005-12-14 | 2007-06-28 | Calsonic Kansei Corp | Vane rotary compressor |
-
2005
- 2005-07-26 CN CNB2005100429910A patent/CN1309810C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4842716A (en) * | 1987-08-13 | 1989-06-27 | Nalco Chemical Company | Ethylene furnace antifoulants |
| CN1218095A (en) * | 1997-11-24 | 1999-06-02 | 中国石油化工总公司 | Coking and scaling inhibitor and preparation and use thereof |
| CN1448490A (en) * | 2002-04-04 | 2003-10-15 | 中国石油化工股份有限公司 | Coking-suppressing antiscale and application thereof |
| JP2007162589A (en) * | 2005-12-14 | 2007-06-28 | Calsonic Kansei Corp | Vane rotary compressor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1712494A (en) | 2005-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1209445C (en) | Method for prepn. of catalytic emulsion | |
| CN1309810C (en) | Coke inhibitor of high-temperature refining equipment | |
| CN1144781C (en) | Monoolefinc C5-mononitriles, method for production and use thereof | |
| CN1283754C (en) | Scale inhibitor of refining equipment | |
| CN1950484A (en) | Hydroprocessing method and system for upgrading heavy oil using a colloidal or molecular catalyst | |
| CN1914216A (en) | Separation of nickel(0) complexes and phosphorus-containing ligands from nitrile mixtures | |
| CN101068881A (en) | Polycarbonate resin composition and molded article thereof | |
| CN1914157A (en) | Continuous method for the production of linear pentene nitriles | |
| CN1600838A (en) | Method for cracking hydrocarbon oil | |
| CN1898362A (en) | Production of low-carbon olefine and arene | |
| CN1210237C (en) | Polymerization-inhibiting composition polymerization inhibitor and method for inhibiting polymerization | |
| CN1926092A (en) | Preparation of sterically hindered hydroxyphenylcarboxylic acid esters | |
| CN1914161A (en) | Production of 3-pentenenitrile from 1,3-butadiene | |
| CN1642887A (en) | Multi-step method of converting a charge containing olefins with four, five or more carbon atoms in order to produce propylene | |
| CN1747922A (en) | Process for producing phenol and methyl ethyl ketone | |
| CN1010413B (en) | Cold rolling oil for steels | |
| CN1767895A (en) | System suitable for the hydrocyanation of olefinically unsaturated compounds. | |
| CN1092078A (en) | Polymer finishing process | |
| CN101469280B (en) | Coking and fouling inhibitor and use method thereof in heavy oil precessing system | |
| CN108165295A (en) | A kind of liquid for oil refining process delayed coking increases income agent | |
| CN1211469C (en) | Coking-suppressing antiscale and application thereof | |
| CN102071047A (en) | Residual oil modifier for coking delaying device and use thereof | |
| CN1778880A (en) | Ethene compressor cleaning media | |
| CN1244669C (en) | Activating additive for delayed coking and cracking heavy oil and preparing method thereof | |
| CN1024504C (en) | Cracking catalyst containing phosphate and hydrogen Y molecular sieve, and its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20070411 |