CN102660320B - Antichlor and preparation method thereof - Google Patents
Antichlor and preparation method thereof Download PDFInfo
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- CN102660320B CN102660320B CN201210157382.XA CN201210157382A CN102660320B CN 102660320 B CN102660320 B CN 102660320B CN 201210157382 A CN201210157382 A CN 201210157382A CN 102660320 B CN102660320 B CN 102660320B
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- dechlorinating agent
- antichlor
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Abstract
The invention relates to antichlor, which belongs to the technical field of fine chemical engineering. The antichlor comprises 20 to 40 percent by weight of aliphatic amine, 30 to 50 percent by weight of alicyclic amine and 10 to 30 percent by weight of alkylol amine. The antichlor is prepared by filtering the raw materials after being uniformly blended to remove impurities. The antichlor is a water soluble flux, has good compatibility with electro-desalting medium, has a synergistic action on the salt content after the electro-desalting of an atmospheric and vacuum distillation unit, has remarkable effect on removing the cchloride ion concentration of drainage and naphtha on top of the device, can effectively improve the corrosion resistance of the device and prolong an on-stream time, is simple to operate and low in cost, and has remarkable economic benefit of the device.
Description
Technical field
The present invention relates to a kind of dechlorinating agent, belong to fine chemical technology field.
Background technology
Atmospheric and vacuum distillation unit has occupied dominant position in oil refining apparatus, and stock oil enters the desalination of electric desalting operation washing breakdown of emulsion after heat exchange, and frequent, underpressure distillation obtains light naphthar, gasoline, diesel oil and mink cell focus.Crude oil is to be mixed by more than 95% carbon, hydrogen compound, and remaining 5% is the organic and inorganic assorted element compound that sulphur, chlorine, nitrogen and metallic element form, though few technique and the quality product that affects whole refinery of this kind compound content.Analyze from the angle of corrosion and corrosion protection erosion, what these impurity that contain in crude oil had itself is exactly corrosive medium, and as hydrogen sulfide, elementary sulfur, mercaptan, organic acid etc., what have can be converted into corrosive medium in the course of processing, the hydrolysis as inorganic salt: MgCl
2+ H
2o=Mg (OH)
2+ 2HCl, CaCl
2+ H
2o=Ca (OH)
2+ 2HCl, etc.
In addition, in crude oil, remove butter and also contain some organic chlorides, the organic chloride having been found that has the tens of kinds of chlorinated hydrocarbons such as trichloromethane, tetracol phenixin, tetrachloroethane, Benzene Chloride, wherein have plenty of in crude oil intrinsic, what have is the paraffin remover that adds of oil recovery process, the clean-out system of course of conveying, and they are broken down into HCl in nearly 30% left and right of air distillation process.
Most refinery adopts secondary desalinating process, and indivedual factories have adopted three grades of desalinating process, makes de-rear salt content in crud oil reach petroleum chemical enterprise's required standard---be less than 3mgNaCl/L.But need explanation here a bit, be that current desalinating process is only to remove water-soluble inorganic salts in crude oil, due to wherein taking the muriate of alkalies and alkaline earth as main, therefore by calcium chloride, magnesium chloride and sodium-chlor are all scaled sodium chloride content and represent with mgNaCl/L, but salt wherein might not be all muriate, also may be vitriol, carbonate and oil hydrochlorate, as found to contain higher petroleum acid calcium in Xinjiang and some crude oil of North China, and muriate also differs, to establish a capital be butter, in crude oil, also contain as previously mentioned hydrochloric ether, these organometallic compounds and hydrochloric ether, current desalinating process can not be removed, they will bring atmospheric tower into, metallic salt will concentrate in residual oil, hydrochloric ether and sulfide part decompose and enter tower top gold-plating and divide and cause corrosion.
Sulphur and chlorine can produce H under existing
2s+HCl+H
2o corrosion, this H
2s+HCl+H
2no matter O corrosion is that general carbon steel or the alloy steel capital cause that under obvious corrosion, particularly high density, both play booster action.Usually there is corrosion failure, affects safety production in device low-temperature section.By reducing erosion rate with inhibiter in filling, but can not fundamentally solve etching problem, in addition divide and directly cause naphtha product cl content to exceed standard because organochlorine enters tower top gold-plating, therefore take efficient manner to reduce or remove organochlorine in crude oil with meet device efficient, steadily and long-term operation to require be a difficult problem anxious to be resolved.
In prior art about the introduction of dechlorinating agent: CN101724435 has introduced the dechlorination method of a kind of oil product or gas, the method comprises that chloride oil product or gas are first passed into one is equipped with the upstream dechlorination tank that does not reach the saturated dechlorinating agent bed of absorption, contact with upstream dechlorination tank by one again and the downstream dechlorination tank of new dechlorinating agent is housed, this method can effectively be utilized the absorption chlorosity of dechlorinating agent, it reached or approach saturated chlorosity, thereby significantly improving the utilization ratio of dechlorinating agent; CN1539921 has introduced a kind of multifunctional dechlorination agent, this dechlorinating agent is a kind of the multiple element compound, wherein contain the binding agent of 0-30 quality %, the molecular sieve of 5-20 quality %, basic metal-alkaline earth metal oxide of 30-90 quality %, the synergistic agent of 1-5 quality %, this dechlorinating agent makes through series of processes such as pre-treatment, total immersion stain, kneading, moulding, roastings, there is the several functions such as dechlorination, desulfurization, denitrogenation simultaneously, can in wide temperature range, in (100-550 DEG C) scope, remove hydrogen chloride gas (< 1 μ g/g).It is dry method dechlorination that two kinds of prior aries enumerating are solid dechlorinating agent, need to increase dry method dechlorination an adsorption device and de-after solid dechlorinating agent need further to process, be only applicable to gaseous state or low viscous petroleum liquid product class, cannot realize operation for high viscosity under this class normal temperature of crude oil.
Summary of the invention
The invention provides a kind of dechlorinating agent and preparation method thereof, enable the organochlorine in effective elimination crude oil, improve the resistance to corrosion of appliance arrangement, and technique is simple, cost is low.
Dechlorinating agent of the present invention is particularly useful for the atmospheric and vacuum distillation unit electric desalting operation in petroleum industry, also can be used in the water filling of atmospheric and vacuum distillation unit tower top or in the tower top water filling of other oil-processing units.
Dechlorinating agent of the present invention, comprises 20～40wt% aliphatic amide, 30～50wt% aliphatic cyclic amine and 10～30wt% hydramine.
As preferred version of the present invention, proportioning raw materials is: 30～40wt% aliphatic amide, 40～50wt% aliphatic cyclic amine and 15～30wt% hydramine.
Described aliphatic amide is selected from Diisopropylamine, isobutylamine, quadrol, 1, and the mixture of one or more arbitrary proportions in 2-propylene diamine is preferably Diisopropylamine and/or 1,2-propylene diamine.
Described aliphatic cyclic amine is selected from the mixture of one or more arbitrary proportions in morpholine, piperazine, hexahydroaniline, is preferably morpholine and/or hexahydroaniline.
Described hydramine is selected from the mixture of one or more arbitrary proportions in Monoethanolamine MEA BASF, diethanolamine, trolamine, preferably Monoethanolamine MEA BASF and/or diethanolamine.
The preparation method of dechlorinating agent of the present invention is: aliphatic amide, aliphatic cyclic amine and hydramine are mixed, then remove by filter impurity, to obtain final product.
Gained oil product dechlorinating agent of the present invention is a kind of water-soluble products, directly join in normal decompression electric desalting washing water filling, dispersed good in water, while applying above-mentioned oil product dechlorinating agent, addition is process raw material 10～100 μ g/g of weight of oil of electric desalting that often reduce pressure, be preferably 15-60 μ g/g, most preferably be 20～30 μ g/g.
The contained soluble chloride auxiliary agent of stock oil has been removed in the time of crude oil electric desalting dewatering, and the chloride auxiliary agent of oil soluble still remains in crude oil.Organic chloride in crude oil is in crude oil atmospheric vacuum distillation process, under the effect of high temperature and water vapour, can resolve into hydrogenchloride, enter normal top and subtract top water of condensation, causing equipment corrosion, this part organic chloride must can be removed by injecting dechlorinating agent when the electrodesalting and electrodehydrating.The synthetic dechlorinating agent of the present invention can with crude oil in organic chloroparaffin by intermolecular effect, oil soluble small molecules organochlorine is converted into water soluble chloride, wash and be transferred to water and deviate from by normal decompression electro-dewatering.Its reaction principle is: because organic chloroparaffin is insoluble to (or being slightly soluble in) water, utilize dechlorinating agent and halohydrocarbon that substitution reaction can occur, the halogen in haloalkane easily by-OH ,-OR ,-CN, NH
3or H
2nR replaces, and generates the water-soluble cpdss such as corresponding alcohol, ether, nitrile, amine, to realize the object removing.
The advantages such as product of the present invention has stable performance, solubility property is superior in stock oil, dispersing property is good, and good with organic chloroparaffin combination stability.
Through 5,000,000 tons/year of atmospheric and vacuum distillation unit industrial tests, test-results shows that the present invention is at stock oil content of organic chloride at 10 to 100 μ g/g in the situation that, and the cl content decreasing ratio that can assurance device enters normal top and subtract top water of condensation reaches 80% to 90%.In atmospheric and vacuum distillation unit electric desalting water filling, add the present invention, can improve the resistance to corrosion of appliance arrangement, extend on-stream time, simple to operate, auxiliary agent cost is low, device remarkable in economical benefits.
Embodiment
Further illustrate content of the present invention below in conjunction with embodiment.
Embodiment 1
First 100g Monoethanolamine MEA BASF is joined in there-necked flask, then add 200g Diisopropylamine and 200g morpholine, under normal temperature, normal pressure, stir after 30min, filtering and impurity removing matter obtain dechlorinating agent A.
Embodiment 2
First 100g diethanolamine is joined in there-necked flask, then add 200g Diisopropylamine, 100g morpholine and 200g piperazine, under normal temperature, normal pressure, stir after 30min, filtering and impurity removing matter obtain dechlorinating agent B.
Embodiment 3
First 100g trolamine is joined in there-necked flask, then add 200g 1,2-propylene diamine, 200g hexahydroaniline stir after 30min under normal temperature, normal pressure, and filtering and impurity removing matter obtain dechlorinating agent C.
Embodiment 4
First 50g Monoethanolamine MEA BASF and 100g diethanolamine are joined in there-necked flask, then add 100g Diisopropylamine, 150g 1,2-propylene diamine and 150g piperazine stir after 30min under normal temperature, normal pressure, and filtering and impurity removing matter obtain dechlorinating agent D.
Table 1 embodiment product typical case performance perameter
Dechlorinating agent evaluation experimental: adopt evaluating of crude oil electric desalting simulation small testing device general in industry, simulate the atmospheric and vacuum distillation unit electric desalting operation in petroleum industry.Use equipment SH-II type electric desalting tester carries out screening and evaluation with static electric field method.The crude oil main character that experiment is used is in table 2:
Table 2 experiment crude oil main character
Concrete test procedure is as follows:
1. draw oil sample and put into the water bath with thermostatic control of 70～90 DEG C, heat-insulation preheating 1h, is poured into the mixed device (PHILIPSHR1704 type stirrer) of adjusting at a high speed, add the water of 6wt%, regulate emulsion strength by controlling stirring velocity and churning time, rotating speed is from 2000～15000r/min, and churning time is 6s.
2. the oil sample mixing is poured in electric desalting device, the emulsion splitter preparing is in advance added respectively to electric desalting device.
3. be raised to after 130 DEG C until electric desalting tester temperature, electric desalting device is put into oil bath cover lid, start preheating switch, hear after buzzer and take out and fluctuate 100 times.
4. electric desalting device after stirring is reentered into oil bath cover lid, opening power startup work knob, carries out low, high pressure desalination (highfield 850V/cm, 2min, weak electric field 350V/cm, 3min, sedimentation 15min).
5. hear after chimes of doom, turn off power switch, take out electric desalting device.
6. the electric desalting device of taking-up is cooled to 60～70 DEG C, opens lower end switchette and emit water, then emit desalination after washing water and crude oil and analyze.
7. get the crude oil sample after step 6 washing desalination after treatment, then carry out the operation of step 1, then the oil sample mixing is poured in electric desalting device, embodiment dechlorinating agent A, B, C, D are added respectively to electric desalting device, then carry out the operation of step 3 to 6.
Test result is in table 3:
Table 3 dechlorinating agent test evaluation result
Can find out and in water filling, add after dechlorinating agent by the test result of table 3, cl content in draining significantly increases, and along with cl content in the increase draining of dechlorinating agent addition increases, when be increased to a certain amount of after in draining cl content tend towards stability, illustrate that oil product dechlorinating agent addition could ensure best effect in certain interval for processing oil property difference.
Oil product dechlorinating agent C described in embodiment 3 is carried out to industrial application experiment at 5,000,000 tons/year of atmospheric and vacuum distillation unit of certain refinery, and the joining day amounts to 30 days, and add-on is that 30 μ g/g(are with respect to raw material).Between the usage period, other main operating parameters and the feedstock property of device remain unchanged.Before using the present invention front and back de-, device three tower top drainings and petroleum naphtha chlorine ion concentration are in table 4.
Table 4 is tested front and the rear three tower top drainings of test and petroleum naphtha chlorine chlorine ion concentration
From three top drainings and petroleum naphtha chlorine ion concentration, before test with test after relatively, just push up, often push up, subtract and push up and petroleum naphtha has declined respectively 72%, 56%, 54%, 85%, successful, has reflected the dechlorination effect of dechlorinating agent from the side.
In sum, oil product dechlorinating agent successful of the present invention, can reduce salts contg after atmospheric and vacuum distillation unit electric desalting effectively, particularly evident for device three tower top drainings and petroleum naphtha chlorine ion concentration removal effect.
Claims (5)
1. a dechlorinating agent, is characterized in that, comprises 30～40wt% aliphatic amide, 40～50wt% aliphatic cyclic amine and 15～30wt% hydramine; Described aliphatic cyclic amine is selected from one or more mixtures with arbitrary proportion composition in morpholine, piperazine, hexahydroaniline; Described aliphatic amide is Diisopropylamine and/or 1,2-propylene diamine.
2. dechlorinating agent as claimed in claim 1, is characterized in that, described aliphatic cyclic amine is morpholine and/or hexahydroaniline.
3. dechlorinating agent as claimed in claim 1, is characterized in that, described hydramine is selected from one or more mixtures with arbitrary proportion composition in Monoethanolamine MEA BASF, diethanolamine, trolamine.
4. dechlorinating agent as claimed in claim 3, is characterized in that, described hydramine is Monoethanolamine MEA BASF and/or diethanolamine.
5. the preparation method of dechlorinating agent described in any one in claim 1 to 4, is characterized in that, aliphatic amide, aliphatic cyclic amine and hydramine are mixed, and then removes by filter impurity, to obtain final product.
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| CN201210157382.XA CN102660320B (en) | 2012-05-18 | 2012-05-18 | Antichlor and preparation method thereof |
Applications Claiming Priority (1)
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|---|---|---|---|
| CN201210157382.XA CN102660320B (en) | 2012-05-18 | 2012-05-18 | Antichlor and preparation method thereof |
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| CN102660320B true CN102660320B (en) | 2014-06-18 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101472634B1 (en) * | 2012-10-29 | 2014-12-15 | 삼성전기주식회사 | Metal nano particle, and method for surface treating the same |
| CN104560126B (en) * | 2013-10-18 | 2018-05-15 | 中国石油化工股份有限公司 | The antichlor and its dechlorination method of chlorion in a kind of removing Reformed Gasoline |
| CN105885934A (en) * | 2015-01-07 | 2016-08-24 | 中石化洛阳工程有限公司 | Lignin hydrodeoxygenation oil dechlorinating process |
| CN114214119A (en) * | 2021-12-27 | 2022-03-22 | 南京多源生物工程有限公司 | Process for reducing chlorine content of anhydrous lanolin |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043954A (en) * | 1989-01-04 | 1990-07-18 | 戈伊特股份公司 | Reduce the method for halogen impurities in the oil product |
| CN102127464A (en) * | 2009-10-22 | 2011-07-20 | 中国石油化工股份有限公司 | Method for removing organochlorine from hydrocarbon oil |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6030523A (en) * | 1997-05-30 | 2000-02-29 | Exxon Research And Engineering Co. | Process for neutralization of petroleum acids (LAW810) |
| CN101597514A (en) * | 2009-06-26 | 2009-12-09 | 天津汇荣石油有限公司 | A kind of technology of crude oil upgrading and reactant thereof |
| CN102433155B (en) * | 2010-09-29 | 2014-01-15 | 中国石油化工股份有限公司 | Method for lightening salt deposition of catalytic fractionating tower |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043954A (en) * | 1989-01-04 | 1990-07-18 | 戈伊特股份公司 | Reduce the method for halogen impurities in the oil product |
| CN102127464A (en) * | 2009-10-22 | 2011-07-20 | 中国石油化工股份有限公司 | Method for removing organochlorine from hydrocarbon oil |
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