CN1069683C - Method for demetal from masrolar D using compound containing sulfur and phosphorus - Google Patents
Method for demetal from masrolar D using compound containing sulfur and phosphorus Download PDFInfo
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- CN1069683C CN1069683C CN97122087A CN97122087A CN1069683C CN 1069683 C CN1069683 C CN 1069683C CN 97122087 A CN97122087 A CN 97122087A CN 97122087 A CN97122087 A CN 97122087A CN 1069683 C CN1069683 C CN 1069683C
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Abstract
The present invention relates to a method for removing metals from hydrocarbon oil by using a compound containing S. P, which uses hydrocarbon oil for being sufficiently mixed with an organic phosphine sulfonic acid compound of which the structure is as the right formula (N-CH2 CH2 (*-CH2 CH2) n-N), water and a demulsifying agent in order to carry out oil-water separation. In the structural formula, n is 0 or 1, X is H or-CH2PO3H2, at least one of A, B, C, D is-RSO3 H and a-RPO3 H2, and the other parts are-RSO3 H,-RPO3 H2 or H. R is an alkyl carbon chain or a hydroxyalkyl carbon chain of C1, C2, C3, C4. The method has the advantages that the metal impurities of Ca, Mg, Fe, etc., can be effectively removed from the hydrocarbon oil, the method can be used for the hydrocarbon oil with high Ca content and low Ca content, the oil-layer layering effect is good, the oil content of the sewerage after removal is low, and the used organic phosphine sulfonic acid compound has low phosphorus content. The present invention is helpful for environmental protection.
Description
The invention belongs to the method for hydrocarbon oil refining, from hydrocarbon ils, remove the method for metallic impurity more precisely with the compound that contains S, P.
Contain multiple metallic element in the crude oil, as Na, Ca, Mg, Fe, Ni, V etc., wherein most of Na and a small amount of Ca, Mg, Fe exist with the form of butter or other inorganic salt, most of Ca, Mg, Fe exist with organic acid salt, phenates form, and Ni, V are then many to be existed with the porphyrins form.Though metal element content is not high in the crude oil, but they are very big to the processing and the use harm of crude oil, for example: after atmospheric and vacuum distillation, the metallic impurity overwhelming majority concentrates in heavy ends and the residual oil, in heavy oil catalytic cracking process, these metallic impurity can be deposited in the catalyst active center, make catalyst deactivation; In hydrofining and hydro-upgrading process, metallic impurity particularly Ca, Fe can with the H that adsorbs on the catalyzer
2The S reaction generates the sulfide deposition on catalyzer, the closed catalyst active centre, and the blocking catalyst bed causes stopping work and catalyst deactivation, and in addition, the too much metallic impurity in the vacuum residuum can increase the ash content in the refinery coke, make the refinery coke downgrade.
After the eighties, begun the research of crude oil and distillate metal remover both at home and abroad, CN86107286A adopts aminocarboxylic acid that hydrocarbon feed is carried out decalcification, CN1036981A adopts di-carboxylic acid and its esters to remove metal from hydrocarbon feed, this two classes metal remover is not because the medicament costliness, is exactly complicated operating process and be difficult to practical application.CN1054261A uses recombiner (comprising precipitation agent ammonium phosphate, emulsion splitter and solid wetting agent ammonium sulfate and oxygen hydroxyl phenol etc.) to remove metal from hydrocarbon ils, CN1055552A removes metal in the hydrocarbon feed with sulfuric acid and salt thereof, the major defect of these two kinds of metal removers is: (1) is difficult for removing compact metal, as calcium naphthenate, phenates etc.; (2) precipitation of Sheng Chenging is easily carried secretly by oil phase, need add precipitating inhibitor and make its water-soluble taking out of; (3) need adjust pH etc.Latest developments in recent years are CN107673A, adopt inorganic poly-phosphorus such as tripoly phosphate sodium STPP to make metal remover; CN110575A makes metal remover with organic phospho acid such as Amino Trimethylene Phosphonic Acid etc.This two classes metal remover is P contained compound, and Ca, Mg, Fe are had good complexing action, and removal effect is better, and the shortcoming of existence is bad to high Ca hydrocarbon ils removal effect, and it is big to deviate from the water oleaginousness, and phosphorus content is higher, is unfavorable for environment protection.In addition, the pyrohydrolysis of inorganic poly-phosphorus tendency is big, and removal efficiency is poor.
It is higher to the objective of the invention is to overcome the prior art phosphorus content, it is big to deviate from the water oleaginousness, be not suitable for the defective of high Ca hydrocarbon ils, provide the low phosphorus compound of a kind of usefulness from hydrocarbon ils, to remove the method for metal, provide a kind of metal removal rate height or rather, the profit layered effect is good, and it is low to deviate from oil content of wastewater, to high Ca and all suitable demetallated method of low Ca hydrocarbon ils.
The compound that usefulness provided by the invention contains S, P removes metal from hydrocarbon ils method comprises: hydrocarbon ils and the compound, water and the emulsion splitter that contain S, P are mixed, carry out oily water separation.The compound that wherein contains S, P is a class organic phosphine sulfonic compound, is selected from compound with following structure and one or more the mixture in the solubility salt thereof specifically:
In the structural formula n be 0 or 13X be H or-CH
2PO
3H
2, have at least one to be-RSO among A, B, C, the D
3H and one-RPO
3H
2, all the other are-RSO
3H or-RPO
3H
2Or H, R is C
1-C
4Alkyl carbon chain or hydroxyalkyl carbochain.More particularly, the compound of the described S of containing, P preferably be selected from following organic phosphine sulfonic and solubility salt thereof, as K
+, Na
+, NH
4 +The mixture of one or more in the salt: (I) quadrol three methene phosphonic acids one hydroxypropyl sulfonic acid (PO
3H
2CH
2)
2-N-CH
2-CH
2 
(II) quadrol two methene phosphonic acids dihydroxypropyl sulfonic acid
(III) quadrol one methylenephosphonic acid three hydroxypropyl sulfonic acid
(IV) diethylenetriamine tetramethyl fork phosphonic acids one hydroxypropyl sulfonic acid
(V) diethylenetriamine three methene phosphonic acids dihydroxypropyl sulfonic acid
(VI) diethylenetriamine two methene phosphonic acids three hydroxypropyl sulfonic acid
With hydrocarbon ils weight is benchmark, and the consumption that contains the compound of S, P is 10-1000ppm, and 50-250ppm preferably also can be according to the metal in the oil, especially Ca, Mg, Fe content and decide, and in general metal content is higher, and the consumption of phosphono and sulfonic also will strengthen.Can be respectively when using phosphono and sulfonic compound and the weight water as the 5-100% of hydrocarbon ils be joined in the hydrocarbon ils, also can earlier phosphono and sulfonic be made into the aqueous solution of 20-60% (wt), mend the 5-100% that adds water to hydrocarbon ils weight then, increase the meltage that water-content in the hydrocarbon ils (comprising the aqueous gross weight of institute in the water of independent adding and the emulsion splitter and the metal remover aqueous solution) helps increasing Ca, thus the raising metal removal effect.But when water-oil ratio surpassed 1: 1, the variation of demetallization per was no longer obvious, and therefore suitable water-content is 5-100%, preferably 10-50%.
Described hydrocarbon ils can be crude oil, fraction oil, normal pressure or vacuum residuum, shale oil, tar sand extract, liquefaction coal, various stock oils or product oil during petrochemical complex is produced, and the mixture of above-mentioned oil product.Before with hydrocarbon ils and water and emulsion splitter mixing, can earlier hydrocarbon ils be preheating to about 60 ℃, make it easy to stir, for the bigger oil of viscosity, also can add light fraction oil or non-polar solvent and dilute viscosity reduction.
The model of described emulsion splitter is to select according to the kind evaluation of hydrocarbon ils, and assessment method is that this area is general, and selected emulsion splitter also is that this area is general, as BP2040, and TP9603 etc.Its consumption is generally the 10-200ppm of hydrocarbon ils weight.
The mode of oily water separation can be hot standing separation, it also can be conventional electric desalting process, or the counter-current extraction process, velocity of separation is faster under electric field action certainly, and general suitable electric-force gradient is 300-1500v/cm, no matter be above-mentioned which kind of separate mode, disengaging time fully separately is as the criterion with profit, and separation temperature is 50-200 ℃, under the identical situation of other conditions, temperature is high more, and oily water separation speed is fast more.
The method that removes metal from hydrocarbon ils provided by the invention has following advantage:
(1) the organic phosphine carboxylic acid compounds of the present invention's use is owing to have-OH-SO simultaneously in the structure
3H ,-PO
3H
2And-four kinds of functional groups of COOH, thereby metals such as Ca, Mg, Fe are had very strong complex ability, organic acid salt that not only can complexing metal, can also strengthen the solubleness of difficulty soluble salt in water greatly, therefore method provided by the invention has good removal effect, can reach more than 85% as the Ca decreasing ratio;
(2) the organic phosphine sulfonic compounds has higher surface activity, and emulsion splitter is had synergistic function, and after electric field separates, the profit layered effect is good, and the interface is clear, and it is low to take off the back oil content of wastewater, and the average specific prior art is hanged down 90ppm, helps environment protection;
(3) organic phosphine sulfonic compounds phosphorus content is low, good stability.The inorganic poly-phosphorus phosphorus content that CN1076473A uses is 30.4%, and 60-150 ℃ of lower section hydrolysis, 70 ℃ of following 50 hours percent hydrolysiss 70% (referring to " petrochemical complex treatment of cooling water technology ", production department of main office of China Petrochemical Industry compiles).The organic phospho acid phosphorus content that CN1120575A uses is 24-31%, average 28.6%.And the organic phosphine sulfonic compounds phosphorus content that the present invention uses is 5.46-20.2%, and is average 13.3%, and stability to hydrolysis good (70 ℃ of following 50 hours percent hydrolysiss are less than 20%), and it is low to take off back sewage phosphorus content, is difficult for causing body eutrophication, favourable to environmental protection.
The invention will be further described below by embodiment.
The organic phosphine sulfonic compounds of selecting for use among the embodiment is the Industrial products of Henan three cyclisation plant produced.
Embodiment 1
On testing laboratory's emulsion splitter competition instrument, carry out.Crude oil is Liaohe River high acid value heavy crude, proportion 0.92g/cm
3, metal content is Ca46.3ppm, Mg1.6ppm, Fe15.4ppm.30g deionized water, 100ppm BP2040 emulsion splitter (BP-2040 type, the production of Mengjin, Luoyang, Henan petrochemical industry impregnating material factory), 200ppm quadrol three methene phosphonic acids, one hydroxypropyl sulfonic acid and the emulsification of 70g crude oil thorough mixing, under 85 ℃, 1000v/cm electric-force gradient, act on 20min, leave standstill, after treating that profit separates fully, measure and take off back crude oil metal content, obtain taking off Ca and lead 95.2%, take off Mg and lead 98.2%, take off Fe and lead 84.3%.Take off oil-containing 90ppm in the water of back.
Embodiment 2
Experiment crude oil is east, Ji crude oil, metal content Ca17.6ppm, Mg1.6ppm, Fe13.3ppm.With 60g crude oil, the 20g aviation kerosene, 6ml deionized water and 50ppm BP2040 emulsion splitter, 40ppm quadrol three methene phosphonic acids one hydroxypropyl azochlorosulfonate acid sodium, 40ppm quadrol one methylenephosphonic acid three hydroxypropyl sulfonic acid, 50-70 ℃ of thorough mixing emulsification, separated 20 minutes down for 95 ℃ in electric-force gradient 1000v/cm, temperature then, after treating that profit separates fully, measure metal content in the oil, calculate demetallization per: take off Ca and lead 95.9%, take off Mg and lead 89.4%, take off Fe and lead 68.5%, take off back oil content of wastewater 95ppm.
Embodiment 3
Adopt the heat mode of leaving standstill to separate.Select the huge port long residuum for use, its metal content is as follows: Ca86.4ppm, Mg0.8ppm, Fe6.1ppm, normal slag of 40g and 40g toluene solvant are pressed 1: 1 mixed, add 350ppm quadrol three methene phosphonic acids one hydroxypropyl sulfonic acid (40% aqueous solution, Henan three cyclisation plant produced), 12ml distilled water, the 100ppmTP-9603 emulsion splitter, thorough mixing emulsification, leave standstill 12h at 90 ℃ of following constant temperature then, make profit separate fully, measure the metal content that takes off back oil, calculate metal removal rate Ca90.1%, Mg90.6%, Fe73.2%.Deviate from water oleaginousness 93ppm.
Embodiment 4
On testing laboratory's emulsion splitter competition instrument, carry out.Test crude oil is selected central plain oil for use, and heavy metal content is Ca67.4ppm, Mg1.65ppm, Fe4.6ppm.With 40g crude oil, 20g aviation kerosene, 20g deionized water, 100ppm BP2040 emulsion splitter, 250ppm quadrol two methene phosphonic acids dihydroxypropyl sodium sulfonates (40% aqueous solution, Henan three cyclisation factories), at 50-70 ℃ of mixing and emulsifying, make it thorough mixing, then at 95 ℃, separate crude oil and water under the 1000v/cm electric-force gradient, back crude oil metal content is taken off in analysis, calculates decalcification rate 92.5%, takes off Mg and leads 87.6%, take off Fe and lead 74.1%, deviate from water oleaginousness 92ppm.
Embodiment 5
Laboratory apparatus and experiment crude oil kind be embodiment 1 roughly the same.With crude oil 40g, 20g aviation kerosene, 20g deionized water, 250ppm diethylenetriamine tetramethyl fork phosphonic acids one hydroxypropyl sulfonic acid, 100ppm TP-9603 emulsion splitter, at 50-70 ℃ of mixing and emulsifying, at 95 ℃, the 1000v/cm electric field action separates crude oil and water down, analyzes metal content, calculate demetallization per: take off Ca and lead 96.1%, take off Mg and lead 97.2%, take off Fe and lead 82.8%, deviate from water oleaginousness 90ppm.
Comparative Examples 1
Experiment condition is with embodiment 4, and (referring to CN1076433A) makes metal remover with Sodium hexametaphosphate 99, records to take off Ca and lead 55.1%, takes off Mg and leads 64.6%, takes off Fe and leads 48.9%, deviates from water oil-containing 240ppm.
Comparative Examples 2
Experiment condition is with embodiment 1, and (referring to CN1076433A) makes metal remover with tripoly phosphate sodium STPP, records to take off Ca and lead 62.1%, takes off Mg and leads 74.6%, takes off Fe and leads 48.9%, deviates from water oil-containing 230ppm.
Comparative Examples 3
Experiment condition is with embodiment 4, and (referring to CN1120575A) is metal remover with the 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid ammonium, records to take off Ca and lead 72.4%, takes off Mg and leads 67.6%, takes off Fe and leads 58.2%, deviates from water oil-containing 190ppm.
Can find that by contrast the metal remover that CN1076433A and CN1120575A adopt is relatively poor to high Ca hydrocarbon ils removal effect, it is big to deviate from the water oleaginousness; And demetallated method provided by the invention all has removal effect preferably to high Ca and low Ca hydrocarbon ils, and it is little to deviate from the water oleaginousness.
Claims (7)
1. from hydrocarbon ils, remove the method for metal with the compound that contains S, P, be that hydrocarbon ils and the compound, water and the emulsion splitter that contain S, P are mixed, carry out oily water separation, it is characterized in that: the compound of the described S of containing, P is selected from compound with following structure and one or more the mixture in the solubility salt thereof:
Wherein n is 0 or 1, X be H or-CH
2PO
3H
2, have at least one to be-RSO among A, B, C, the D
3H and one-RPO
3H
2, all the other are-RSO
3H or-RPO
3H
2Or H, R is C
1～C
4Alkyl carbon chain or hydroxyalkyl carbochain, be benchmark with hydrocarbon ils weight, consumption is 10～1000ppm.
2. according to the described demetallated method of claim 1, it is characterized in that the described S of containing, P-compound are selected from one or more the mixture in following compound and the water soluble salt thereof:
(I) quadrol three methene phosphonic acids one hydroxypropyl sulfonic acid
(II) quadrol two methene phosphonic acids dihydroxypropyl sulfonic acid
(III) quadrol one methylenephosphonic acid three hydroxypropyl sulfonic acid
(IV) diethylenetriamine tetramethyl fork phosphonic acids one hydroxypropyl sulfonic acid
(V) diethylenetriamine three methene phosphonic acids dihydroxypropyl sulfonic acid
(VI) diethylenetriamine two methene phosphonic acids three hydroxypropyl sulfonic acid
3. according to the described demetallated method of claim 1, it is characterized in that described hydrocarbon ils comprises crude oil, normal pressure or vacuum residuum and distillate.
4. according to the described demetallated method of claim 1, it is characterized in that oily water separation is to carry out under 50～200 ℃, the electric field action of 300～1500v/cm.
5. according to the described demetallated method of claim 1, the consumption that it is characterized in that water is 5～100% of a hydrocarbon ils weight.
6. according to the described demetallated method of claim 5, the consumption that it is characterized in that water is 5～50% of a hydrocarbon ils weight.
7. according to the described demetallated method of claim 1, it is characterized in that the emulsion splitter consumption is 10～200ppm of hydrocarbon ils weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122087A CN1069683C (en) | 1997-12-23 | 1997-12-23 | Method for demetal from masrolar D using compound containing sulfur and phosphorus |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97122087A CN1069683C (en) | 1997-12-23 | 1997-12-23 | Method for demetal from masrolar D using compound containing sulfur and phosphorus |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1221018A CN1221018A (en) | 1999-06-30 |
| CN1069683C true CN1069683C (en) | 2001-08-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97122087A Expired - Lifetime CN1069683C (en) | 1997-12-23 | 1997-12-23 | Method for demetal from masrolar D using compound containing sulfur and phosphorus |
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Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1208434C (en) * | 2003-06-03 | 2005-06-29 | 克拉玛依市金山石油化工有限公司 | Hydrocarbon oil demetalizing agent, and preparing method and use method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1160458A (en) * | 1915-01-14 | 1915-11-16 | Worcester Metal Goods Company | Catch for travelling-bags. |
| FR1018187A (en) * | 1950-05-19 | 1952-12-29 | Languedocienne De Rech S Et D | Improvements to processes for separating mineral substances by flotation |
| CN1036981A (en) * | 1988-03-07 | 1989-11-08 | 切夫尔昂研究公司 | From hydrocarbon feed, remove metal with di-carboxylic acid and its esters |
| CN1054261A (en) * | 1991-02-06 | 1991-09-04 | 中国石油化工总公司 | From hydrocarbon feed, remove metal with recombiner |
| CN1120575A (en) * | 1994-10-14 | 1996-04-17 | 王中亭 | Removal of metal from oil with organic phospho acid and its salt |
-
1997
- 1997-12-23 CN CN97122087A patent/CN1069683C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1160458A (en) * | 1915-01-14 | 1915-11-16 | Worcester Metal Goods Company | Catch for travelling-bags. |
| FR1018187A (en) * | 1950-05-19 | 1952-12-29 | Languedocienne De Rech S Et D | Improvements to processes for separating mineral substances by flotation |
| CN1036981A (en) * | 1988-03-07 | 1989-11-08 | 切夫尔昂研究公司 | From hydrocarbon feed, remove metal with di-carboxylic acid and its esters |
| CN1054261A (en) * | 1991-02-06 | 1991-09-04 | 中国石油化工总公司 | From hydrocarbon feed, remove metal with recombiner |
| CN1120575A (en) * | 1994-10-14 | 1996-04-17 | 王中亭 | Removal of metal from oil with organic phospho acid and its salt |
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| Publication number | Publication date |
|---|---|
| CN1221018A (en) | 1999-06-30 |
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