CN105802659A - Environment-friendly composite crude oil decalcifying agent - Google Patents
Environment-friendly composite crude oil decalcifying agent Download PDFInfo
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- CN105802659A CN105802659A CN201610294712.8A CN201610294712A CN105802659A CN 105802659 A CN105802659 A CN 105802659A CN 201610294712 A CN201610294712 A CN 201610294712A CN 105802659 A CN105802659 A CN 105802659A
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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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/28—Organic compounds not containing metal atoms containing sulfur as the only hetero atom, e.g. mercaptans, or sulfur and oxygen as the only hetero atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C10G29/00—Refining of hydrocarbon oils, in the absence of hydrogen, with other chemicals
- C10G29/20—Organic compounds not containing metal atoms
- C10G29/26—Halogenated hydrocarbons
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to an environment-friendly composite crude oil decalcifying agent which is prepared from the following components in percentage by mass: 20-60wt% of a chelating agent, 5-20wt% of an organic acid, 20-40wt% of a dispersant, 0.1-5wt% of a surfactant, 0.5-3wt% of a corrosion inhibitor and 10-40wt% of water. The environment-friendly composite crude oil decalcifying agent does not contain phosphorus; due to introduction of an amino acid structure, the environment-friendly composite crude oil decalcifying agent has relatively good biological degradability and is a novel environment-friendly crude oil decalcifying agent. By the decalcifying agent, over 90% of calcium in crude oil can be eliminated; the decalcifying agent does not contain a eutrophic element phosphorus and is environmentally friendly.
Description
Technical field
The present invention relates to a kind of environment-friendly type composite crude oil decalcifying agent, belong to the crude oil preconditioning technique field in oil Refining Technologies field.
Background technology
A calcium part in crude oil exists with water soluble salt, the slightly soluble salt such as form such as calcium chloride, calcium bicarbonate, calcium sulfate, calcium phosphate, and another part exists with the form of petroleum acids calcium.The electro-desalting process of oil plant generally can remove salt and the hydrophilic inorganic calcium salt granule of most solubility；But for being present in lipophile inorganic calcium salt granule in oil phase and petroleum acids calcium then almost without removal effect, the processing of follow-up crude oil is had serious harm by this part metals calcium.Research shows, in catalytic cracking process, doped calcium on a catalyst, can limit contacting of hydrocarbon molecule and catalyst, even make catalyst poisoning permanent deactivation；High calcium content makes selectivity of catalyst change, thus causing that catalytic cracking product distribution also changes therewith, yield of light oil reduces, and makes the economic benefit that oil product is processed be greatly reduced.
Existing chemical method crude oil decalcifying technology substantially can be attributed to chemistry acid treatment decalcification method, chemical precipitation decalcification method and chelating decalcification method.The disclosed crude oil decalcifying technology such as CN1112424C, CN1454967A belongs to chemistry acidic treatment, this kind of technology is the petroleum acids calcium principle utilized in organic or inorganic in the strong acid displacement crude oil calcium to remove in crude oil, this type of method shortcoming is that the industrial acids environment adopted is unfriendly, to industrial equipment seriously corroded, it is necessary to select corrosion resistant apparatus；The disclosed crude oil decalcifying technology such as CN1055552A, CN1054261A, CN1078234C belongs to chemical precipitation method, this kind of method adopts water soluble sulfate, phosphate, phosphoric acid hydrogen disalt to generate slightly soluble or water-fast calcium sulfate, calcium phosphate, calcium bicarbonate with the petroleum acids effect in crude oil, under the effect of solid wetting agent, it is deposited on aqueous phase reaches the purpose of decalcification, the shortcoming of this kind of decalcification method is that calcium removal efficiency is not high, the easy occluding device pipeline of precipitate produced, the industrial residue simultaneously produced needs to process, and environmental pollution is serious.The disclosed crude oil decalcifying technology such as CN1076473, CN87105863, CN86107286, CN1657594 belongs to chemistry chelating method, the employing of these methods can generate the amino carboxylic acid of water soluble chelate compound, dicarboxylic acids, hydroxy carboxylic acid etc. with calcium and carry out crude oil decalcifying, the medicament price comparison that the shortcoming of this type of method is used is expensive, it is difficult to industrialization.To sum up, existing decalcifying agent can't well meet industry needs, so, the decalcifying agent developing a kind of high-efficiency environment friendly will produce significant economic benefit and social environment benefit in oil refining process.
Summary of the invention
Technical problem: it is an object of the invention to provide a kind of environment-friendly type composite crude oil decalcifying agent.This decalcifying agent decalcification rate is high, not phosphorous, and environmental friendliness uses safety.
Technical scheme: a kind of environment-friendly type composite crude oil decalcifying agent, formed by by the following component at room temperature mixed preparing of example in mass ratio: 20～60wt% chelating agen, 5～20wt% organic acid, 20～40wt% dispersant, 0.1～5wt% surfactant, 0.5～3wt% corrosion inhibiter, the water of 10～40wt%.
The chelating agen used in above-mentioned crude oil decalcifying agent is to be undertaken free-radical polymerized by polyether amino acid ester reaction monomers, itaconic acid and the unsaturated double-bond monomer containing vinyl and obtain, and its general structure is:
Wherein: A be containing vinyl unsaturated double-bond monomer copolymerization after constitutional repeating unit, degree of polymerization x is 2～500, and degree of polymerization y is 2～500, and degree of polymerization z is 2～500, and repetitive m is 3～100.
The preparation method of above-mentioned environment-friendly type composite crude oil decalcifying agent preparation chelating agen used is:
At N2Under atmosphere, room temperature, quality in allyloxy Polyethylene Glycol monoether, the methionine of allyloxy Polyethylene Glycol monoether and 0.1～5 times of allyloxy Polyethylene Glycol monoether quality is added mixing in reactor, it is 2～5 with 5～10wt% salt acid for adjusting pH, microwave reaction 0.1～1h, microwave power is 80～800W, continues reaction 1～5h at 50～140 DEG C after microwave reaction, it is cooled to room temperature, obtains polyether amino acid ester reaction monomers；Itaconic acid by 0.1～6 times of allyloxy Polyethylene Glycol monoether quality, 0.1～6 times of allyloxy Polyethylene Glycol monoether quality containing vinyl unsaturated double-bond monomer, the chain-transferring agent of 0.02～0.5 times of allyloxy Polyethylene Glycol monoether quality and the distilled water of 0.2～6 times of allyloxy Polyethylene Glycol monoether quality add in reactor, the inorganic initiator of 0.02～0.6 times of allyloxy Polyethylene Glycol monoether quality is dripped with uniform speed, this inorganic initiator concentration is mass percentage concentration is the aqueous solution of 0.2～20wt%, 0.5～3h drips off, continue after dripping off to react 1～8h at 60～95 DEG C, it is down to room temperature 25 DEG C, obtaining solid content is the chelating agen of 20～60wt%.
The above-mentioned environment-friendly type composite crude oil decalcifying agent preparation monomer containing vinyl unsaturated double-bond described in chelating agen preparation method used is acrylamide or maleic anhydride；Described inorganic initiator is Ammonium persulfate. or persulfonic acid sodium；Described chain-transferring agent is TGA or isopropanol.
Above-mentioned one or more the combination that environment-friendly type composite crude oil decalcifying agent preparation organic acid used is acetic acid, citric acid or sulfamic acid.
Above-mentioned environment-friendly type composite crude oil decalcifying agent preparation dispersant used is one or more the combination in maleic acrylic copolymer, hydrolytic polymaleic anhydride, polyacrylic acid or maleic acid/acrylic acid/hydroxyethylacrylate copolymer.
Above-mentioned environment-friendly type composite crude oil decalcifying agent preparation surfactant used is one or more arbitrary proportion mixture in sodium lauryl sulphate, Dodecyl trimethyl ammonium chloride or butyl glycol ether；Corrosion inhibiter is the mixture of one or more arbitrary proportions in hexamethylenamine, hexamethylenetetramine or thiourea.
Beneficial effect: a kind of environment-friendly type composite crude oil decalcifying agent of the present invention has following excellent properties:
(1) this environment-friendly type composite crude oil decalcifying agent is not phosphorous, and amino acid structure introduces and makes it have better biological degradability, is a kind of novel environmental protection crude oil decalcifying agent.
(2) this environment-friendly type crude oil decalcifying agent has taken into full account the synergism between different group in preparation process, abundant carboxyl contained in chelating agen, amino and ether, calcium in the carboxyl contained and amino group energy chelating crude oil, and formed cyclic chelate there is water solublity；The hydrophilic of ether makes the calcium chelate of formation soluble in water, it is easy to separate, and uses technique simple；S and N element with the hydrogen evolution hydrogen bond in water, can make the calcium ion tolerance of this decalcifying agent be greatly improved, the calcium in crude oil had efficient removal effect simultaneously..
(3) organic acid that compound process is chosen contains carboxyl, sulfonic acid group can improve sequestering power and sulfonic group can avoid carboxylic acid copolymer higher in self concentration or cation concn produces the defect of gel compared with relative superiority or inferiority；Containing substantial amounts of carboxyl and ester group in dispersant, it is possible to improve the sequestering power of decalcifying agent and increase oil water contact area, improving removal efficiency；Surfactant can change oil water interfacial tension, improves the contact probability of decalcifying agent molecule and oil-soluble calcium；The introducing of corrosion inhibiter then can reduce the corrosion of equipment and pipeline, the service life of extension device.
The performance test methods of above-mentioned a kind of environment-friendly type composite crude oil decalcifying agent is:
Experiment oil is the peaceful pipe oil transportation in Shandong, and calcium content is 20～30ppm, iron content 6.0～9.0ppm.By 40g crude oil, the water filling and the 40ppm demulsifier FC9300 phase that account for its mass fraction 8wt% mix, 0.5h is preheated at 80 DEG C, then stir 5 minutes with the intensity of 1800r/min in agitator, it is transferred in electrical desalter, crude oil decalcifying agent is added than 4.5: 1 (mass ratioes) according still further to agent calcium, according to certain desalting in oil refinery workshop section execute-in-place condition, electro-desalting experimental condition is defined as: the electro-desalting temperature of 125 DEG C, highfield intensity is 1500V/cm, the time of staying is 3～10 minutes, weak electric field intensity is 400V/cm, the time of staying is 5～12 minutes, sedimentation time is 30 minutes.Gather in electrical desalter after profit is completely separated de-after crude oil, in de-rear crude oil, the analysis method of tenor is referring to the GB/T508-91 method in " Petrochemical Engineering Analysis method ", carry out pretreatment by dry ash method, measure with plasma emission spectroscopy, record decalcification rate and deferrization rate.
Detailed description of the invention
Embodiment 1: at N2Atmosphere, at 25 DEG C, 100g allyloxy Polyethylene Glycol monoether and 30g methionine are added mixing in reactor, it is 2.5 with 10wt% salt acid for adjusting pH, microwave reaction 0.1h, microwave power is 100W, reaction 2h is continued at 95 DEG C after microwave reaction, weigh 25g itaconic acid, 20g maleic anhydride, 5g TGA and 300g distilled water again and add mixing in reactor, after being cooled to 85 DEG C, the ammonium persulfate aqueous solution of dropping 50g4wt%, 2h drips off, after dropwising, continue to react 3h at 85 DEG C, after being down to 25 DEG C, obtain the transparent chelating agen A of brownish red.
Environment-friendly type composite crude oil decalcifying agent is according to above-mentioned chelating agen A35g, acetic acid 20g, polyacrylic acid 20g, sodium lauryl sulphate 2g, hexamethylenamine 1g, 22g deionized water, and at room temperature 25 DEG C, mixed preparing forms.With Shandong, peaceful pipe oil transportation is experiment crude oil, and its calcium content is 26.7ppm, and iron content is 7.5ppm, and gained environment-friendly type composite crude oil decalcifying agent is when dosage is 120ppm, and decalcification rate is 97.5%, and deferrization rate is 61.3%.
Embodiment 2: at N2Atmosphere, at 25 DEG C, 120g allyloxy Polyethylene Glycol monoether, 30g methionine are added mixing in reactor, it is 3.5 with 10wt% salt acid for adjusting pH, microwave reaction 0.3h, microwave power is 300W, reaction 4h is continued at 75 DEG C after microwave reaction, weigh 50g itaconic acid, 30g acrylamide, 15g isopropanol and 350g distilled water again and add mixing in reactor, after being warming up to 85 DEG C, the persulfonic acid sodium water solution of dropping 50g6wt%, 1h drips off, after dropwising, continue to react 6h at 85 DEG C, after being down to 25 DEG C, obtain the transparent chelating agen B of brownish red.
The preparation of environment-friendly type composite crude oil decalcifying agent: by above-mentioned chelating agen B40g, citric acid 15g, hydrolytic polymaleic anhydride 25g, Dodecyl trimethyl ammonium chloride 1g, hexamethylene tetramine 2g, 17g deionized water, mixed preparing forms at 25 DEG C.With Shandong, peaceful pipe oil transportation is experiment crude oil, and its calcium content is 25.3ppm, and iron content is 6.8ppm, and gained environment-friendly type composite crude oil decalcifying agent is when dosage is 114ppm, and decalcification rate is 98.3%, and deferrization rate is 64.9%.
Embodiment 3: at N2Atmosphere, at 25 DEG C, 100g allyloxy Polyethylene Glycol monoether and 35g methionine are added mixing in reactor, it is 4.5 with 15wt% salt acid for adjusting pH, microwave reaction 0.5h, microwave power is 500W, reaction 6h is continued at 80 DEG C after microwave reaction, weigh 45g itaconic acid, 30g maleic anhydride, 15g TGA and 400g distilled water again and add mixing in reactor, after being warming up to 85 DEG C, the persulfonic acid sodium water solution of dropping 50g8wt%, after 1.5h dropwises, continues to react 6h at 85 DEG C, after being down to 25 DEG C, obtain the transparent chelating agen C of brownish red.
The preparation of environment-friendly type composite crude oil decalcifying agent: by above-mentioned chelating agen C25g, sulfamic acid 15g, maleic acrylic copolymer 25g, butyl glycol ether 1.5g, thiourea 2.5g, 31g deionized water, mixed preparing forms at 25 DEG C.With Shandong, peaceful pipe oil transportation is experiment crude oil, and its calcium content is 27.9ppm, and iron content is 7.3ppm, and gained environment-friendly type composite crude oil decalcifying agent is when dosage is 125ppm, and decalcification rate is 97.8%, and deferrization rate is 68.4%.
Embodiment 4: at N2Atmosphere, at 25 DEG C, 150g allyloxy Polyethylene Glycol monoether and 40g methionine are added mixing in reactor, it is 4 with 15wt% salt acid for adjusting pH, microwave reaction 1h, microwave power is 800W, reaction 5h is continued at 100 DEG C after microwave reaction, weigh 50g itaconic acid, 40g maleic anhydride, 25g isopropanol and 400g distilled water again and add mixing in reactor, after being cooled to 90 DEG C, the persulfonic acid sodium water solution of dropping 50g10wt%, after 3h dropwises, continues to react 10h at 90 DEG C, after being down to 25 DEG C, obtain the saturating chelating agen D of brownish red.
The preparation of environment-friendly type composite crude oil decalcifying agent: by above-mentioned chelating agen D25g, sulfamic acid 10g, acetic acid 10g, citric acid 5g, maleic acrylic copolymer 10g, polyacrylic acid or maleic acid/acrylic acid/hydroxyethylacrylate copolymer 10g, butyl glycol ether 1.5g, Dodecyl trimethyl ammonium chloride 1g, thiourea 1.5g, hexamethylenamine 1g, 25g deionized water, at 25 DEG C, mixed preparing forms.With Shandong peaceful pipe oil transportation be experiment crude oil, its calcium content is 29.4ppm, iron content be 8.3ppm gained environment-friendly type composite crude oil decalcifying agent when dosage is 132ppm, decalcification rate is 99.3%, and deferrization rate is 70.3%.
Embodiment 5: at N2Atmosphere, at 25 DEG C, 200g allyloxy Polyethylene Glycol monoether and 60g methionine are added mixing in reactor, it is 5 with 10wt% salt acid for adjusting pH, microwave reaction 0.6h, microwave power is 600W, reaction 6h is continued at 95 DEG C after microwave reaction, weigh 70g itaconic acid, 30g acrylamide, 15g isopropanol and 350g distilled water again and add mixing in reactor, after being cooled to 70 DEG C, the persulfonic acid sodium water solution of dropping 40g10wt%, after 2.5h dropwises, continues to react 8h at 70 DEG C, after being down to 25 DEG C, obtain the saturating chelating agen E of brownish red.
The preparation of environment-friendly type composite crude oil decalcifying agent: by above-mentioned chelating agen E30g, sulfamic acid 15g, citric acid 5g, polyacrylic acid or maleic acid/acrylic acid/hydroxyethylacrylate copolymer 20g, Dodecyl trimethyl ammonium chloride 2g, hexamethylene tetramine 1.5g, hexamethylenamine 1g, 25.5g deionized water, at 25 DEG C, mixed preparing forms.With Shandong peaceful pipe oil transportation be experiment crude oil, its calcium content is 28.6ppm, iron content be 7.9ppm gained environment-friendly type composite crude oil decalcifying agent when dosage is 128ppm, decalcification rate is 97.6%, and deferrization rate is 65.9%.
Claims (8)
1. an environment-friendly type composite crude oil decalcifying agent, it is characterized in that this decalcifying agent is at room temperature to be formed by following component example mixed preparing in mass ratio: 20～60wt% chelating agen, 5～20wt% organic acid, 20～40wt% dispersant, 0.1～5wt% surfactant, 0.5～3wt% corrosion inhibiter, the water of 10～40wt%.
2. environment-friendly type composite crude oil decalcifying agent as claimed in claim 1, it is characterized in that this crude oil decalcifying agent preparation chelating agen used is to be undertaken free-radical polymerized by polyether amino acid ester reaction monomers, itaconic acid and the unsaturated double-bond monomer containing vinyl and obtain, its general structure is:
Wherein: A be containing vinyl unsaturated double-bond monomer copolymerization after constitutional repeating unit, degree of polymerization x is 2～500, and degree of polymerization y is 2～500, and degree of polymerization z is 2～500, and repetitive m is 3～100.
3. environment-friendly type composite crude oil decalcifying agent as claimed in claim 2, it is characterised in that the preparation method of described chelating agen is:
At N2Under atmosphere, room temperature, quality in allyloxy Polyethylene Glycol monoether, the methionine of allyloxy Polyethylene Glycol monoether and 0.1～5 times of allyloxy Polyethylene Glycol monoether quality is added mixing in reactor, it is 2～5 with 5～10wt% salt acid for adjusting pH, microwave reaction 0.1～1h, microwave power is 80～800W, continues reaction 1～5h at 50～140 DEG C after microwave reaction, it is cooled to room temperature, obtains polyether amino acid ester reaction monomers；Itaconic acid by 0.1～6 times of allyloxy Polyethylene Glycol monoether quality, 0.1～6 times of allyloxy Polyethylene Glycol monoether quality containing vinyl unsaturated double-bond monomer, the chain-transferring agent of 0.02～0.5 times of allyloxy Polyethylene Glycol monoether quality and the distilled water of 0.2～6 times of allyloxy Polyethylene Glycol monoether quality add in reactor, the inorganic initiator of 0.02～0.6 times of allyloxy Polyethylene Glycol monoether quality is dripped with uniform speed, this inorganic initiator concentration is mass percentage concentration is the aqueous solution of 0.2～20wt%, 0.5～3h drips off, continue after dripping off to react 1～8h at 60～95 DEG C, it is down to room temperature 25 DEG C, obtaining solid content is the chelating agen of 20～60wt%.
4. environment-friendly type composite crude oil decalcifying agent as claimed in claim 3, it is characterised in that the monomer containing vinyl unsaturated double-bond described in the preparation method of described chelating agen is acrylamide or maleic anhydride；Described inorganic initiator is Ammonium persulfate. or persulfonic acid sodium；Described chain-transferring agent is TGA or isopropanol.
5. a kind of environment-friendly type composite crude oil decalcifying agent according to claim 1, it is characterised in that one or more the combination that organic acid is acetic acid, citric acid, sulfamic acid that the preparation of this decalcifying agent is used.
6. a kind of environment-friendly type composite crude oil decalcifying agent according to claim 1, it is characterised in that the dispersant used by the preparation of this decalcifying agent is one or more the combination in maleic acrylic copolymer, hydrolytic polymaleic anhydride, polyacrylic acid, maleic acid/acrylic acid/hydroxyethylacrylate copolymer.
7. a kind of environment-friendly type composite crude oil decalcifying agent according to claim 1, it is characterised in that the surfactant used by the preparation of this decalcifying agent is one or more arbitrary proportion mixture in sodium lauryl sulphate, Dodecyl trimethyl ammonium chloride or butyl glycol ether.
8. a kind of environment-friendly type composite crude oil decalcifying agent according to claim 1, it is characterised in that the described corrosion inhibiter used by the preparation of this decalcifying agent is one or more the mixture in hexamethylenamine, hexamethylenetetramine, thiourea.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106433745A (en) * | 2016-09-14 | 2017-02-22 | 中国海洋石油总公司 | High-adaptability low-corrosion decalcifying agent of crude oil |
| CN106496455A (en) * | 2016-10-21 | 2017-03-15 | 中国海洋石油总公司 | A kind of method for improving crude oil decalcifying agent low-temperature stability |
| CN106867572A (en) * | 2017-03-15 | 2017-06-20 | 东南大学 | A kind of compound without phosphorus crude oil metal-chelator |
| CN110643386A (en) * | 2019-09-20 | 2020-01-03 | 南京江宇新材料科技有限公司 | Compound crude oil metal chelating agent |
| CN112322339A (en) * | 2020-10-19 | 2021-02-05 | 南京江宇新材料科技有限公司 | Crude oil metal chelating agent and preparation method thereof |
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| CN106433745A (en) * | 2016-09-14 | 2017-02-22 | 中国海洋石油总公司 | High-adaptability low-corrosion decalcifying agent of crude oil |
| CN106433745B (en) * | 2016-09-14 | 2018-02-16 | 中国海洋石油总公司 | A kind of crude oil decalcifying agent of high-adaptability low corrosion |
| CN106496455A (en) * | 2016-10-21 | 2017-03-15 | 中国海洋石油总公司 | A kind of method for improving crude oil decalcifying agent low-temperature stability |
| CN106496455B (en) * | 2016-10-21 | 2018-12-11 | 中国海洋石油集团有限公司 | A method of improving crude oil decalcifying agent low-temperature stability |
| CN106867572A (en) * | 2017-03-15 | 2017-06-20 | 东南大学 | A kind of compound without phosphorus crude oil metal-chelator |
| CN110643386A (en) * | 2019-09-20 | 2020-01-03 | 南京江宇新材料科技有限公司 | Compound crude oil metal chelating agent |
| CN110643386B (en) * | 2019-09-20 | 2021-08-13 | 南京江宇新材料科技有限公司 | Compound crude oil metal chelating agent |
| CN112322339A (en) * | 2020-10-19 | 2021-02-05 | 南京江宇新材料科技有限公司 | Crude oil metal chelating agent and preparation method thereof |
| CN112322339B (en) * | 2020-10-19 | 2023-02-28 | 南京江宇新材料科技有限公司 | Crude oil metal chelating agent and preparation method thereof |
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