CN106398748B - A kind of method of hydrocarbon ils deferrization agent and hydrocarbon ils deferrization - Google Patents
A kind of method of hydrocarbon ils deferrization agent and hydrocarbon ils deferrization Download PDFInfo
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Abstract
The present invention relates to hydrocarbon ils deferrization fields, disclose a kind of hydrocarbon ils deferrization agent, and the hydrocarbon ils deferrization agent contains organic acid, polyether modified silicon oil, thiamines ester and/or sulphur nitrogen ester and solvent.A kind of method of hydrocarbon ils deferrization is also disclosed, the method includes：Under the conditions of electro-desalting, hydrocarbon ils is contacted with hydrocarbon ils deferrization agent and carries out deferrization, the hydrocarbon ils deferrization agent is hydrocarbon ils deferrization agent as described above.The hydrocarbon ils deferrization agent of the present invention, has good removal effect to the iron in hydrocarbon ils, equally applicable to the hydrocarbon ils of high Fe content, can effectively remove the oil-soluble iron in hydrocarbon ils and non-oil-soluble iron, will not cause the Local enrichment of de- rear metals in hydrocarbon oil；The deferrization agent dosage of the present invention is low, effect is good, using simple, by existing Process Conditions for Electrostatic Desalting while desalting and dewatering, you can the efficient removal for realizing metallic iron is easy to commercial introduction application.
Description
Technical field
The present invention relates to hydrocarbon ils deferrization fields, and in particular, to a kind of hydrocarbon ils deferrization agent and using the hydrocarbon ils deferrization agent into
The method of row hydrocarbon ils deferrization.
Background technology
In recent years, with the exploitation of the unconventional energy resource such as fine and close oil, shale oil and crude oil with poor quality and Residual cracking amount
It is continuously increased, metals in hydrocarbon oil content ascensional range is larger, increasingly prominent for following process and the harm used.Wherein iron pair
Catalytic cracking unit, the toxic action of heavy oil hydrogenation equipment catalyst are larger, and catalyst can be made to cohere and build up, lead to catalyst
Structure is destroyed, inactivation, fluidizes exception, or even generates permanent poisoning, and iron can also promote atmospheric and vacuum distillation column overhead and condensed system
The burn into furnace tubing of system and heat exchange equipment fouling etc..Therefore, it is necessary to carry out deferrization to hydrocarbon ils.
Iron in hydrocarbon ils can be divided into oil-soluble iron and non-oil-soluble iron, the analysis method of iron type referring to《Crude oil and slag
Fe content distributions and its existing forms in oil》(high prosperous etc., petroleum journal (PETROLEUM PROCESSING), the 2nd phase of volume 30, in April, 2014)
Middle 1.4.1 subtracts oil-soluble iron content by total iron content and obtains water-soluble iron content, more precisely should be non-oil-soluble iron and contains
It measures (including iron precipitate not soluble in water).
It has been recognized that the key of chemical method deferrization is to convert oil-soluble iron to non-oil-soluble by adding deferrization agent
Iron, the excessively conventional electric desalting water washing method of non-oil-soluble Tie Tong can remove.Therefore, prior art research emphasis is oil-soluble iron
Removing.Patent CN1982413A describes a kind of metal remover being made of organic carboxyl acid and organic phospho acid；
CN101314728A describes a kind of method of hydrocarbons raw oil deferrization, is formed using nitrogenous compound and organic acid mixed preparing
Deferrization agent, have stronger iron ion sequestering power；Crude oil metal remover is by sulphonic acids disclosed in patent CN103937529A
Compound, ammonium salt, isocyanates, corrosion inhibiter and solvent composition；Crude oil metal remover disclosed in CN101215477A by carbonic ester,
Organic acid, nonionic surfactant, chelating agent, carbamide compounds and solvent composition.Deferrization agent disclosed above is for crude oil
Oil-soluble iron has good removal effect.
The salt contained by the water in oil is scattered in emulsified state however, generally also having in hydrocarbon ils, and is suspended in oil
Superfine ferrous mineral particle, these non-oil-soluble iron are easy to the emulsion highly stable with grease System forming, and
And with the increasing of oil extraction difficulty, and the unconventional energy resource such as fine and close oil, shale oil exploitation, non-oil-soluble iron in hydrocarbon ils
Content increases, and conventional electric desalting water washing method is difficult to be removed.In addition, the hydrocarbon ils rich in oil-soluble iron uses conventional deferrization agent
Afterwards, oil-soluble iron is changed into non-oil-soluble iron compound, but water phase may not necessarily be transferred to completely, the upper layer crude oil typically resulted in
Iron content is substantially reduced, and nearby crude oil iron content is still very high for rag layer, illustrates that non-oil-soluble iron is not removed effectively,
Therefore it develops new and effective deferrization agent and deferrization method is most important.
Invention content
The purpose of the present invention is to solve deferrization agent deferrization effect in the prior art is poor, it is particularly difficult to remove in hydrocarbon ils
The problem of non-oil-soluble iron, provides a kind of new hydrocarbon ils deferrization agent, and the method for carrying out hydrocarbon ils deferrization using the hydrocarbon ils deferrization agent.
The present inventor has found that hydrocarbon ils deferrization agent contains organic acid, polyether modified silicon oil, thiamines ester under study for action
And/or sulphur nitrogen ester and solvent, deferrization rate can be improved, the oil-soluble iron in hydrocarbon ils and non-oil-soluble iron can be effectively removed.
Therefore, to achieve the goals above, on the one hand, the present invention provides a kind of hydrocarbon ils deferrization agent, the hydrocarbon ils deferrization
Agent contains organic acid, polyether modified silicon oil, thiamines ester and/or sulphur nitrogen ester and solvent.
Preferably, on the basis of the total weight of the hydrocarbon ils deferrization agent, the content of organic acid is 5-30 weight %, and polyethers changes
Property silicone oil content be 10-50 weight %, the total content of thiamines ester and sulphur nitrogen ester is 5-30 weight %, and the content of solvent is 10-
50 weight %；It is highly preferred that on the basis of the total weight of the hydrocarbon ils deferrization agent, the content of organic acid is 5-30 weight %, is gathered
The sum of content of ether modified silicon oil, thiamines ester and sulphur nitrogen ester is 40-60 weight %, and the content of solvent is 20-50 weight %.
Preferably, the organic acid is oxalic acid, maleic acid, citric acid, 1-hydroxy ethylidene-1,1-diphosphonic acid and 2- hydroxy phosphinylidyne base second
At least one of acid.
Preferably, the thiamines ester is O- isopropyl-N- ethyl thionic carbamates and/or O- isobutyl group-N- allyls
Base thionic carbamate, the sulphur nitrogen ester are N, N- dimethyl dithiocarbamic acids methyl esters and/or N, N- di-n-butyl two
Methyl thiocarbamate.
Preferably, the solvent be alcohol and water mixed solution, alcohol be methanol, ethyl alcohol, ethylene glycol and isopropanol in extremely
The weight ratio of few one kind, alcohol and water is 1:2-4.
Preferably, the content of iron is 10-300ug/g in the hydrocarbon ils that the hydrocarbon ils deferrization agent is applied.
Preferably, the hydrocarbon ils be mineral oil and its distillate, more preferably crude oil, residual oil, deasphalted oil, shale oil,
At least one of fine and close oil and liquefied coal coil.
Second aspect, the present invention also provides a kind of method of hydrocarbon ils deferrization, the method includes：In electro-desalting condition
Under, hydrocarbon ils is contacted with hydrocarbon ils deferrization agent and carries out deferrization, the hydrocarbon ils deferrization agent is hydrocarbon ils deferrization agent as described above.
Preferably, relative to 1g hydrocarbon ils, the dosage of the hydrocarbon ils deferrization agent is 10-1000 μ g, more preferably 20-300 μ g,
Still more preferably it is 80-150 μ g.
Preferably, the electro-desalting condition includes：Electrostatic field temperature is 100-150 DEG C, electric field strength 200-2000V/
Cm, more preferably 300-1000V/cm.
The hydrocarbon ils deferrization agent of the present invention, has good removal effect to the iron in hydrocarbon ils, same to the hydrocarbon ils of high Fe content
It is applicable in, can effectively remove the oil-soluble iron in hydrocarbon ils and non-oil-soluble iron, the part of de- rear metals in hydrocarbon oil will not be caused rich
Collection；The deferrization agent dosage of the present invention is low, effect is good, using simple, by existing Process Conditions for Electrostatic Desalting in the same of desalting and dewatering
When, you can the efficient removal for realizing metallic iron is easy to commercial introduction application.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
On the one hand, the present invention provides a kind of hydrocarbon ils deferrization agent, which contains organic acid, polyether-modified silicon
Oil, thiamines ester and/or sulphur nitrogen ester and solvent.
In the present invention, it is preferable that on the basis of the total weight of hydrocarbon ils deferrization agent, the content of organic acid is 5-30 weight %,
The content of polyether modified silicon oil is 10-50 weight %, and the total content of thiamines ester and sulphur nitrogen ester is 5-30 weight %, the content of solvent
For 10-50 weight %；It is highly preferred that on the basis of the total weight of hydrocarbon ils deferrization agent, the content of organic acid is 5-30 weight %, is gathered
The sum of content of ether modified silicon oil, thiamines ester and sulphur nitrogen ester is 40-60 weight %, and the content of solvent is 20-50 weight %.At this
Under preferable case, deferrization rate can be further increased.
In the present invention, when hydrocarbon ils deferrization agent i.e. containing thiamines ester again containing sulphur nitrogen ester when, for the respective content of the two without
Particular/special requirement, as long as the sum of the content of the two meets above-mentioned requirements.
In the present invention, organic acid is preferably oxalic acid, maleic acid, citric acid, 1-hydroxy ethylidene-1,1-diphosphonic acid and 2- hydroxy phosphinylidyne bases
At least one of acetic acid.
In the present invention, polyether modified silicon oil is that polyethers and a kind of organosilicon made of dimethyl silicone polymer graft copolymerization are non-
Ionic surface active agent has low surface tension and good wetting, permeance property, in of the invention, for polyether modified silicon oil
Without particular/special requirement, polyether modified silicon oil commonly used in the art may be used, for example, may be used YNE series, XHG series,
The polyether modified silicon oils such as Silok series.
In the present invention, thiamines ester refers to that the sulfydryl in xanthic acid molecule is replaced by alkyl amino, i.e. thionic amino
Formic acid esters, in of the invention, various thiamines esters commonly used in the art, preferably O- isopropyls-N- ethyl sulphur may be used in thiamines ester
By carbamateAnd/or O- isobutyl group-N- allyl sulfides are by carbamateSulphur nitrogen ester be refer to sulphur nitrogen class collecting agent metal ion by alkyl or
The derivative of alkyl replaces, i.e. dithiocarbamates, and in the present invention, sulphur nitrogen ester may be used commonly used in the art each
Kind sulphur nitrogen ester, preferably N, N- dimethyl dithiocarbamic acid methyl estersAnd/or bis- positive fourth of N, N-
Base aminodithioformic acid methyl esters
In the present invention, solvent is preferably the mixed solution of alcohol and water, and alcohol is preferably methanol, ethyl alcohol, ethylene glycol and isopropanol
At least one of, the weight ratio of alcohol and water is preferably 1:2-4.
In the present invention, " hydrocarbon ils that hydrocarbon ils deferrization agent is applied " refers to the hydrocarbon ils deferrization agent progress deferrization for being applicable in the present invention
Hydrocarbon ils, hydrocarbon ils deferrization agent of the invention be suitable for the higher hydrocarbon ils of iron content, for example, the present invention hydrocarbon ils deferrization agent applied
Hydrocarbon ils in the content of iron can be 10-300ug/g.For hydrocarbon ils type without particular/special requirement, such as can be mineral oil and
Its distillate, such as at least one of crude oil, residual oil, deasphalted oil, shale oil, fine and close oil and liquefied coal coil.
The preparation method of the hydrocarbon ils deferrization agent of the present invention can be obtained hydrocarbon without particular/special requirement, as long as each component is uniformly mixed
Oily deferrization agent.
Second aspect, the present invention also provides a kind of method of hydrocarbon ils deferrization, this method includes：Under the conditions of electro-desalting,
Hydrocarbon ils is contacted with hydrocarbon ils deferrization agent and carries out deferrization, the hydrocarbon ils deferrization agent is hydrocarbon ils deferrization agent as described above.
In the present invention, relative to 1g hydrocarbon ils, the dosage of hydrocarbon ils deferrization agent is preferably 10-1000 μ g, more preferably 20-300 μ
G is still more preferably 80-150 μ g.
In the present invention, electro-desalting condition preferably includes：Electrostatic field temperature is 100-150 DEG C, electric field strength 200-
2000V/cm, more preferably 300-1000V/cm.
In the present invention, in order to make the iron in hydrocarbon ils preferably remove, in order to make hydrocarbon ils deferrization agent preferably play a role,
It is preferred that demulsifier is added in hydrocarbon ils, deferrization is then carried out again, for example, distillation can be added after 70-90 DEG C preheats hydrocarbon ils
Then water and demulsifier carry out deferrization again.For demulsifier dosage without particular/special requirement, the use of this field routine may be used
Amount, for example, relative to 1g hydrocarbon ils, the dosage of demulsifier can be 40-60 μ g.
The hydrocarbon ils deferrization method of the present invention can carry out in conventional Crude Desalting System, such as former agent injection may be used
Mode deferrization agent is mixed with hydrocarbon ils, decanting point is referred to the injection mode of demulsifier, can both be injected into mixing valve or
Feed line before static mixer can also be injected into electro-desalting waterflood-transmission lines at different levels, the electricity for being 100-150 DEG C into temperature
Desalter after staying for some time, carries out water-oil separating under electric field action, in hydrocarbon ils the metallic elements such as iron enter water phase or
Water phase aggregate and precipitate, into sewerage.
Embodiment
The present invention is further illustrated for embodiment below, but is not intended to limit the present invention.
In the following Examples and Comparative Examples：
The method for measuring iron content in oil sample：GB/T 18608-2012
It is original total in deferrization rate=(in hydrocarbon ils after original total iron content-deferrization in oil sample to be measured iron content)/hydrocarbon ils
Iron content × 100%
Preparation example 1
This preparation example is used to illustrate the hydrocarbon ils deferrization agent of the present invention.
By the citric acid of 5 parts by weight, YNE5211 (being purchased from Nanjing Yi Nuoen Chemical Co., Ltd.s), 30 weights of 15 parts by weight
The water for measuring the O- isopropyl-N- ethyl thionics carbamate of part, the ethyl alcohol of 12.5 parts by weight and 37.5 parts by weight is uniformly mixed,
Obtain hydrocarbon ils deferrization agent A1.
Preparation example 2
This preparation example is used to illustrate the hydrocarbon ils deferrization agent of the present invention.
By the maleic acid of 15 parts by weight, YNE408 (being purchased from Nanjing Yi Nuoen Chemical Co., Ltd.s), 20 weights of 20 parts by weight
O- isobutyl group-N- the allyl sulfides for measuring part are uniformly mixed by the water of carbamate, the methanol of 15 parts by weight and 30 parts by weight, are obtained
To hydrocarbon ils deferrization agent A2.
Preparation example 3
This preparation example is used to illustrate the hydrocarbon ils deferrization agent of the present invention.
By the oxalic acid of 30 parts by weight, the Silok2235 (being purchased from Guangzhou Si Luoke Chemical Co., Ltd) of 40 parts by weight, 10
The water of the O- isopropyl-N- ethyl thionics carbamate of parts by weight, the isopropanol of 4 parts by weight and 16 parts by weight is uniformly mixed,
Obtain hydrocarbon ils deferrization agent A3.
Preparation example 4
This preparation example is used to illustrate the hydrocarbon ils deferrization agent of the present invention.
By the Silok2250 of the 1-hydroxy ethylidene-1,1-diphosphonic acid of 5 parts by weight, 15 parts by weight, (being purchased from Guangzhou Si Luoke chemistry has
Limit company), the N of 30 parts by weight, N- dimethyl dithiocarbamic acids methyl esters, the ethylene glycol of 12.5 parts by weight and 37.5 parts by weight
Water be uniformly mixed, obtain hydrocarbon ils deferrization agent A4.
Preparation example 5
This preparation example is used to illustrate the hydrocarbon ils deferrization agent of the present invention.
The XHG248 of the 2- hydroxyphosphonoacetic acid of 15 parts by weight, 30 parts by weight (is purchased from Zhejiang and newly pacifies Chemical Group stock
Part Co., Ltd), the N of 25 parts by weight, N- second, n-butyl dithiocarbamates methyl esters, the methanol of 10 parts by weight and 20 parts by weight
Water be uniformly mixed, obtain hydrocarbon ils deferrization agent A5.
Preparation example 6
This preparation example is used to illustrate the hydrocarbon ils deferrization agent of the present invention.
The XHG278 of the citric acid of 20 parts by weight, 40 parts by weight (is purchased from Zhejiang and newly pacifies the limited public affairs of Chemical Group share
Department), the N of 20 parts by weight, the water mixing of N- dimethyl dithiocarbamic acids methyl esters, the isopropanol of 4 parts by weight and 16 parts by weight
Uniformly, hydrocarbon ils deferrization agent A6 is obtained.
Preparation example 7
This preparation example is used to illustrate the hydrocarbon ils deferrization agent of the present invention.
Hydrocarbon ils deferrization agent is prepared according to the method for preparation example 3, unlike, the dosage of Silok2235 is 20 parts by weight, different
The dosage of propyl alcohol is 8 parts by weight, and the dosage of water is 32 parts by weight, obtains hydrocarbon ils deferrization agent A7.
Compare preparation example 1
By the 1-hydroxy ethylidene-1,1-diphosphonic acid of 30 parts by weight, the citric acid of 30 parts by weight, the ethyl alcohol of 10 parts by weight and 30 parts by weight
Water be uniformly mixed, obtain hydrocarbon ils deferrization agent D1.
Embodiment 1
The present embodiment is used to illustrate the hydrocarbon ils deferrization method of the present invention.
It takes 100g hydrocarbon ils A, B, C (property is shown in Table 1) to be respectively put into 150mL beakers respectively, and respectively proceeds as follows：
After being preheated at 80 DEG C, 10g distilled water is added and 5mg demulsifiers (are purchased from Guangzhou Zhenqing Environmental Technology Co., Ltd., GT-D06 crude oil
Demulsifier, similarly hereinafter), 10mg hydrocarbon ils deferrization agent A1 are added, are uniformly mixed, be then sealed against being placed on 120 DEG C, electric field strength be
30min is handled in the electrostatic field of 500V/cm and carries out water-oil separating, 80 DEG C are cooled the temperature to after processing, takes upper layer oil sample (oil respectively
The oil sample of layer the top 1cm thickness) and middle level oil sample (oil sample of the above 1cm thickness of oil-water interfaces layer) measurement iron content, and point
Not Ji Suan deferrization rate, be denoted as upper layer deferrization rate and middle level deferrization rate, the results are shown in Table 2.
Embodiment 2
The present embodiment is used to illustrate the hydrocarbon ils deferrization method of the present invention.
It takes 100g hydrocarbon ils A, B, C (property is shown in Table 1) to be respectively put into 150mL beakers respectively, and respectively proceeds as follows：
After being preheated at 70 DEG C, 10g distilled water and 4mg demulsifiers is added, 8mg hydrocarbon ils deferrization agent A2 are added, is uniformly mixed, it is then that its is close
It is honored as a queen and is placed in 100 DEG C, processing 30min progress water-oil separatings in the electrostatic field that electric field strength is 300V/cm, drop temperature after processing
To 70 DEG C, taking upper layer oil sample (oil sample of oil reservoir the top 1cm thickness) and middle level oil sample respectively, (the above 1cm of oil-water interfaces layer is thick
The oil sample of degree) iron content is measured, and deferrization rate is calculated separately, it is denoted as upper layer deferrization rate and middle level deferrization rate, the results are shown in Table 2.
Embodiment 3
The present embodiment is used to illustrate the hydrocarbon ils deferrization method of the present invention.
It takes 100g hydrocarbon ils A, B, C (property is shown in Table 1) to be respectively put into 150mL beakers respectively, and respectively proceeds as follows：
After being preheated at 90 DEG C, 10g distilled water and 6mg demulsifiers is added, 15mg hydrocarbon ils deferrization agent A3 are added, is uniformly mixed, then by it
Processing 30min carries out water-oil separating in the electrostatic field that sealing is placed on 150 DEG C, electric field strength is 700V/cm, by temperature after processing
90 DEG C are down to, takes upper layer oil sample (oil sample of oil reservoir the top 1cm thickness) and middle level oil sample (the above 1cm of oil-water interfaces layer respectively
The oil sample of thickness) iron content is measured, and deferrization rate is calculated separately, it is denoted as upper layer deferrization rate and middle level deferrization rate, the results are shown in Table 2.
Embodiment 4
The present embodiment is used to illustrate the hydrocarbon ils deferrization method of the present invention.
It takes 100g hydrocarbon ils A, B, C (property is shown in Table 1) to be respectively put into 150mL beakers respectively, and respectively proceeds as follows：
After being preheated at 85 DEG C, 10g distilled water and 5mg demulsifiers is added, 9mg hydrocarbon ils deferrization agent A4 are added, is uniformly mixed, it is then that its is close
It is honored as a queen and is placed in 110 DEG C, processing 30min progress water-oil separatings in the electrostatic field that electric field strength is 1000V/cm, by temperature after processing
85 DEG C are down to, takes upper layer oil sample (oil sample of oil reservoir the top 1cm thickness) and middle level oil sample (the above 1cm of oil-water interfaces layer respectively
The oil sample of thickness) iron content is measured, and deferrization rate is calculated separately, it is denoted as upper layer deferrization rate and middle level deferrization rate, the results are shown in Table 2.
Embodiment 5
The present embodiment is used to illustrate the hydrocarbon ils deferrization method of the present invention.
It takes 100g hydrocarbon ils A, B, C (property is shown in Table 1) to be respectively put into 150mL beakers respectively, and respectively proceeds as follows：
After being preheated at 75 DEG C, 10g distilled water and 4mg demulsifiers is added, 11mg hydrocarbon ils deferrization agent A5 are added, is uniformly mixed, then by it
Processing 30min carries out water-oil separating in the electrostatic field that sealing is placed on 130 DEG C, electric field strength is 800V/cm, by temperature after processing
75 DEG C are down to, takes upper layer oil sample (oil sample of oil reservoir the top 1cm thickness) and middle level oil sample (the above 1cm of oil-water interfaces layer respectively
The oil sample of thickness) iron content is measured, and deferrization rate is calculated separately, it is denoted as upper layer deferrization rate and middle level deferrization rate, the results are shown in Table 2.
Embodiment 6
The present embodiment is used to illustrate the hydrocarbon ils deferrization method of the present invention.
It takes 100g hydrocarbon ils A, B, C (property is shown in Table 1) to be respectively put into 150mL beakers respectively, and respectively proceeds as follows：
After being preheated at 80 DEG C, 10g distilled water and 6mg demulsifiers is added, 13mg hydrocarbon ils deferrization agent A6 are added, is uniformly mixed, then by it
Processing 30min carries out water-oil separating in the electrostatic field that sealing is placed on 140 DEG C, electric field strength is 600V/cm, by temperature after processing
80 DEG C are down to, takes upper layer oil sample (oil sample of oil reservoir the top 1cm thickness) and middle level oil sample (the above 1cm of oil-water interfaces layer respectively
The oil sample of thickness) iron content is measured, and deferrization rate is calculated separately, it is denoted as upper layer deferrization rate and middle level deferrization rate, the results are shown in Table 2.
Embodiment 7
The present embodiment is used to illustrate the hydrocarbon ils deferrization method of the present invention.
Hydrocarbon ils deferrization is carried out according to the method for embodiment 3, unlike, the hydrocarbon ils deferrization agent of addition is hydrocarbon ils deferrization agent
A7.It the results are shown in Table 2.
Comparative example 1
Hydrocarbon ils deferrization is carried out according to the method for embodiment 1, unlike, the hydrocarbon ils deferrization agent of addition is hydrocarbon ils deferrization agent
D1.It the results are shown in Table 2.
Comparative example 2
Hydrocarbon ils deferrization is carried out according to the method for embodiment 1, unlike, it is added without hydrocarbon ils deferrization agent.It the results are shown in Table 2.
Table 1
Table 2
Embodiment 1 is compared with comparative example 1-2 respectively as can be seen that being not added with the sky of hydrocarbon ils deferrization agent in comparative example 2
Under the conditions of white, deferrization rate is low, and upper layer deferrization rate is apparently higher than middle level, illustrates that iron is unevenly distributed in de- rear hydrocarbon ils, especially hydrocarbon ils B
Middle level deferrization rate be negative value, illustrate that de- middle level iron content afterwards increases instead, metallic iron be enriched in middle level oil phase and not completely into
Enter water phase；Although the existing organic acid hydrocarbon ils deferrization agent of comparative example 1 can improve deferrization rate, deferrization rate in upper layer is de- with middle level
Iron rate difference is larger, the problem of iron is enriched in the hydrocarbon ils of middle level is equally existed, moreover, the non-oil-soluble iron of hydrocarbon ils A accounts for total iron
The non-oil-soluble iron of 25.4%, hydrocarbon ils B account for the 66.2% of total iron, and the non-oil-soluble iron of hydrocarbon ils C accounts for the 90.4% of total iron, with non-
The ratio that oil-soluble iron accounts for total iron is bigger, and the middle level deferrization rate of comparative example 1 is lower, illustrates that existing hydrocarbon ils deferrization agent cannot be effective
Remove non-oil-soluble iron；And hydrocarbon ils deferrization agent using the present invention carries out deferrization, no matter for the high hydrocarbon of non-oil-soluble iron content
Oil, or for the low hydrocarbon ils of non-oil-soluble iron content, high deferrization rate is all had, and deferrization rate in upper layer connects with middle level deferrization rate
Closely, illustrate that de- rear metallic iron is distributed more uniformly in hydrocarbon ils, most of iron is transferred to water phase removing, and hydrocarbon ils of the invention is de-
Chalybeate can effectively remove oil-soluble iron and non-oil-soluble iron in hydrocarbon ils.
Embodiment 3 and embodiment 7 are compared and can be seen that on the basis of the total weight of hydrocarbon ils deferrization agent, organic acid
Content be 5-30 weight %, polyether modified silicon oil, thiamines ester and sulphur nitrogen ester the sum of content be 40-60 weight %, solvent
Content is 20-50 weight %, can further increase deferrization rate.
The hydrocarbon ils deferrization agent of the present invention, has good removal effect to the iron in hydrocarbon ils, same to the hydrocarbon ils of high Fe content
It is applicable in, can effectively remove the oil-soluble iron in hydrocarbon ils and non-oil-soluble iron, the part of de- rear metals in hydrocarbon oil will not be caused rich
Collection；The deferrization agent dosage of the present invention is low, effect is good, using simple, by existing Process Conditions for Electrostatic Desalting in the same of desalting and dewatering
When, you can the efficient removal for realizing metallic iron is easy to commercial introduction application.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (12)
1. a kind of hydrocarbon ils deferrization agent, which is characterized in that the hydrocarbon ils deferrization agent contains organic acid, polyether modified silicon oil, thiamines ester
And/or sulphur nitrogen ester and solvent；
On the basis of the total weight of the hydrocarbon ils deferrization agent, the content of organic acid is 5-30 weight %, and polyether modified silicon oil contains
It is 10-50 weight % to measure, and the total content of thiamines ester and sulphur nitrogen ester is 5-30 weight %, and the content of solvent is 10-50 weight %；
The organic acid is at least one in oxalic acid, maleic acid, citric acid, 1-hydroxy ethylidene-1,1-diphosphonic acid and 2- hydroxyphosphonoacetic acid
Kind；
The thiamines ester is O- isopropyl-N- ethyl thionic carbamates and/or O- isobutyl group-N- allyl sulfides by amino first
Acid esters, the sulphur nitrogen ester are N, N- dimethyl dithiocarbamic acids methyl esters and/or N, N- second, n-butyl dithiocarbamate
Methyl esters；
Polyether modified silicon oil is polyethers and organosilicon nonionic surfactant made of dimethyl silicone polymer graft copolymerization.
2. hydrocarbon ils deferrization agent according to claim 1, wherein organic on the basis of the total weight of the hydrocarbon ils deferrization agent
The content of acid is 5-30 weight %, polyether modified silicon oil, thiamines ester and sulphur nitrogen ester the sum of content be 40-60 weight %, solvent
Content be 20-50 weight %.
3. hydrocarbon ils deferrization agent according to claim 1 or 2, wherein the solvent is the mixed solution of alcohol and water, and alcohol is first
The weight ratio of at least one of alcohol, ethyl alcohol, ethylene glycol and isopropanol, alcohol and water is 1:2-4.
4. hydrocarbon ils deferrization agent according to claim 1 or 2, wherein iron in the hydrocarbon ils that the hydrocarbon ils deferrization agent is applied
Content is 10-300 μ g/g.
5. hydrocarbon ils deferrization agent according to claim 4, wherein the hydrocarbon ils is mineral oil and its distillate.
6. hydrocarbon ils deferrization agent according to claim 5, wherein the hydrocarbon ils be crude oil, residual oil, deasphalted oil, shale oil,
At least one of fine and close oil and liquefied coal coil.
7. a kind of method of hydrocarbon ils deferrization, which is characterized in that the method includes：Under the conditions of electro-desalting, by hydrocarbon ils and hydrocarbon ils
Deferrization agent contact carries out deferrization, and the hydrocarbon ils deferrization agent is the hydrocarbon ils deferrization agent described in any one of claim 1-6.
8. according to the method described in claim 7, wherein, relative to 1g hydrocarbon ils, the dosage of the hydrocarbon ils deferrization agent is 10-1000
μg。
9. according to the method described in claim 8, wherein, relative to 1g hydrocarbon ils, the dosage of the hydrocarbon ils deferrization agent is 20-300 μ
g。
10. according to the method described in claim 9, wherein, relative to 1g hydrocarbon ils, the dosage of the hydrocarbon ils deferrization agent is 80-150
μg。
11. according to the method described in claim 7, wherein, the electro-desalting condition includes：Electrostatic field temperature is 100-150 DEG C,
Electric field strength is 200-2000V/cm.
12. according to the method for claim 11, wherein the electric field strength is 300-1000V/cm.
Priority Applications (1)
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| CN110564446A (en) * | 2018-06-05 | 2019-12-13 | 中国石油化工股份有限公司 | Dirty oil treating agent and application thereof and method for recycling dirty oil |
| CN113171584B (en) * | 2021-04-26 | 2022-07-01 | 天津海成能源工程技术有限公司 | Iron removing liquid and method for removing iron ions of high-boiling residues of VCM device |
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| US20130306310A1 (en) * | 2012-05-16 | 2013-11-21 | Darrell Lynn Gallup | Pipeline reaction for removing heavy metals from produced fluids |
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| CN1982412A (en) * | 2005-12-15 | 2007-06-20 | 中国石油化工股份有限公司 | Method for removing metal impurities from hydrocarbon raw material |
| CN101353591A (en) * | 2007-07-26 | 2009-01-28 | 中国石油化工股份有限公司 | Composite desalter and use method thereof |
| CN101851525A (en) * | 2009-10-20 | 2010-10-06 | 新疆德蓝股份有限公司 | Preparation of organic silicon petroleum de-emulsifier |
| US20130306310A1 (en) * | 2012-05-16 | 2013-11-21 | Darrell Lynn Gallup | Pipeline reaction for removing heavy metals from produced fluids |
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