CN104629791A - Cyclic utilization method of complexation-method crude-oil decalcified discharge liquid - Google Patents
Cyclic utilization method of complexation-method crude-oil decalcified discharge liquid Download PDFInfo
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- CN104629791A CN104629791A CN201310571914.9A CN201310571914A CN104629791A CN 104629791 A CN104629791 A CN 104629791A CN 201310571914 A CN201310571914 A CN 201310571914A CN 104629791 A CN104629791 A CN 104629791A
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- Prior art keywords
- decalcifying
- crude oil
- ammonium
- calcium
- cyclic utilization
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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
-
- 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
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2300/80—Additives
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a cyclic utilization method of complexation-method crude-oil decalcified discharge liquid. The method comprises the following steps: reacting waste water produced after decalcification between ammonium citrate and crude oil with an ammonium salt solution of a strong precipitant; separating calcium precipitant produced in reaction liquid; mixing the separated clear liquid with a supplementary fresh decalcifying agent to be used as the decalcifying agent for renewed cyclic utilization; abandoning the separated solid residues or further separating and utilizing, wherein the ammonium salt of the strong precipitant is selected from ammonium carbonate, ammonium phosphate or diammonium hydrogen phosphate; the input mass of the ammonium salt of the strong precipitant is 90-99 percent of the mass of calcium precipitant which is produced through theoretically complete reaction. According to the cyclic utilization method of the complexation-method crude-oil decalcified discharge liquid, the production cost of an ammonium citrate crude oil decalcifying process can be effectively reduced, and the processing cost of decalcified waste water is greatly reduced; moreover, the cyclic utilization method has a good economic benefit, can be combined with a crude oil electro-desalting process of a refinery plant, can be applied to industrial decalcifying continuous production of calcium-containing crude oil, and has a good application prospect.
Description
Technical field
The present invention relates to technical field of petrochemical industry, more particularly, relate to the recycle of the complexometry crude oil decalcifying relief liquor of crude oil complete processing.
Background technology
A calcium metal part in crude oil exists with water-soluble salt, slightly soluble salt such as the inorganic calcium salt such as calcium chloride, calcium sulfate form, and another part then exists with organic calcium salt forms such as petroleum acid calcium.For salt and the hydrophilic inorganic calcium salt particle of solubility, refinery adopts simple water-washing method to remove usually in electric desalting process, but for the petroleum acid calcium be present in oil phase, this rule does not almost have removal effect, and the crude oil of existence to postorder of this part of calcium salt adds trade union and produces many negative impacts.
Chelating decalcification method also claims complexing decalcification method, is the one of crude oil decalcifying method, and it adopts the chemical agent that can generate water soluble complex with the Ca in crude oil to carry out crude oil decalcifying.Ammonium citrate is a kind of environmentally friendly harmless environmental type decalcifying agent.Apply this decalcifying agent, when the calcium contents in crude oil is lower, because using dosage is few, decalcifying agent can be ignored lower water mitigation; And for the higher crude oil of calcium content, because the ammonia-nitrogen content in water under decalcification is higher, it affects greatly the process of service water, simultaneously, decalcifying agent superfluous in lower water also can be wasted, and therefore, significant is reclaimed in the process this decalcifying agent being produced to lower water.
Summary of the invention
The object of the invention is the circulation utilization method proposing a kind of complexometry crude oil decalcifying relief liquor, carry out process for ammonium citrate at the lower water that crude oil decalcifying process produces to reclaim, its Ethylene recov can be used as the recycle of regeneration decalcifying agent, reduce crude oil decalcifying cost, avoid or reduce the discharge of water under decalcification.
The method that the present invention proposes is, by the lower water that ammonium citrate and crude oil decalcifying effect produce, with the ammonium salt solution effect of strong precipitation agent, in lower water, the calcium salt of citric acid is reduced into ammonium citrate, produce the throw out of calcium simultaneously, solid-liquid separation is carried out to solution, the ammonium citrate containing decalcification surplus in the liquid of separation and the ammonium citrate reduced by precipitating action, itself and the fresh decalcifying agent supplemented are converged, as decalcifying agent again recycle; The solid slag be separated is thrown aside or further extraction and application.
The ammonium salt of strong precipitation agent is selected to calcium in conjunction with the corresponding ammonium salt of the compound that solubility product is very little, as volatile salt, ammonium phosphate, Secondary ammonium phosphate etc.The compound of carbanion, phosphate anion, phosphoric acid hydrogen radical ion and calcium binding is calcium carbonate, calcium phosphate, secondary calcium phosphate respectively, and 25.15 DEG C time, their solubility products in water are respectively: 2.8 × 10
-9, 2.0 × 10
-29, 1.0 × 10
-7, without in other ion interference situation, calcium carbonate, calcium phosphate, secondary calcium phosphate are dissolved in calcium ion content in water at below 50ug/g, illustrate that their corresponding negative valency ion pair calcium ions have strong precipitating action.
The ammonium salt input amount of strong precipitation agent should calculate according to the concentration of calcium ion contained in lower water, the strong precipitation agent dropped into is slightly less than the theoretical amount of complete reaction generation needed for calcium deposit, general in 90% ~ 99% of theoretical amount, the ammonium salt of excessive strong precipitation agent is avoided to enter decalcification technique, can except the middle most of calcium ion that anhydrates.
The solid-liquid separation of solution, according to the needs of operating mode, can be separated by intermittent type standing sedimentation, also can carry out continuously centrifuged separation, rotary filter press or swash plate separation etc., needs also can carry out multistage continuous solid-liquid separation according to technique.In the supernatant liquor be separated, institute's calcium ions comparatively descends water to decline to a great extent, and ammonium citrate content increases, like this, supernatant liquor has just possessed the basis of recycle, by ion chromatography ammonium citrate content wherein, supplement appropriate fresh decalcifying agent wherein, to reach the requirement of decalcifying agent add-on, this liquid circulation decalcification utilizes.Obtain solid slag how many according to its moisture content, or directly throw aside, or further degree of depth solid-liquid separation, recycled.
The circulation utilization method of the complexometry crude oil decalcifying relief liquor that the present invention proposes, effectively can reduce the production cost of ammonium citrate crude oil decalcifying technique, under decalcification, cost of water treatment significantly reduces, good in economic efficiency.
The present invention can be combined with refinery's crude oil electric desalting technique, is applied to the industrial decalcification continuous seepage of Crude Oil, has a good application prospect.
Accompanying drawing explanation
Fig. 1 embodiment 2 process flow sheet.
Embodiment
With embodiment, the present invention is further described below.
Embodiment 1:
Get 1 ton, water under the electric desalting of ammonium citrate crude oil decalcifying, survey calcium ion content 936ug/g in its water, Xiang Shuizhong adds volatile salt 2.09kg, abundant mixing, left standstill through 16 hours, surveying calcium ion content in supernatant liquor is 105ug/g, ammonium citrate content is 3610ug/g, get supernatant liquor 900 kilograms, in this supernatant liquor, add ammonium citrate 1251g, reach the decalcifying agent implantation concentration requirement that ammonium citrate content is 5000ug/g, this liquid is the decalcifying agent of processing requirement, can crude oil decalcifying effect be carried out, complete the recycle of decalcification relief liquor.
Embodiment 2:
Technical process as shown in Figure 1, in figure, 1 is electrical desalter, and 2 is mixing tank, and 3 is two-stage wet cyclone.Under electric desalting, discharge is 10 tons/hour, survey calcium ion content 1060ug/g in its water, concentration be 10% the ammonium dibasic phosphate aqueous solution flow that enters mixing tank be 332.3kg/ hour, precipitin reaction is there is in mixing tank, compound enters two-stage wet cyclone, the calcium slag obtained bottom wet cyclone is thrown aside, the supernatant liquor be separated is flowed out by second stage wet cyclone, flow is 9.6 tons/hour, in clear liquid, calcium ion content is 120ug/g, ammonium citrate content is 4238ug/g, the ammonium citrate decalcifying agent replenisher of 10% is injected in this supernatant liquor pipeline, flow control is at 73.15kg/ hour, the ammonium citrate content of now decalcifying agent reuse pipeline is about 5000ug/g, be the requirement concentration that decalcifying agent injects, decalcifying agent basin can be introduced into stand-by.
Claims (2)
1. the circulation utilization method of a complexometry crude oil decalcifying relief liquor, it is characterized in that: the lower water that ammonium citrate and crude oil decalcifying effect are produced, with the ammonium salt solution effect of strong precipitation agent, the Ca-deposit produced in effect liquid is separated, isolated clear liquid converges, as decalcifying agent again recycle with the fresh decalcifying agent supplemented; The solid slag be separated is thrown aside or further extraction and application;
The ammonium salt of described strong precipitation agent selects volatile salt, ammonium phosphate or Secondary ammonium phosphate;
It is that complete reaction generates the quality 90% ~ 99% of calcium deposit in theory that the ammonium salt of strong precipitation agent drops into quality.
2. the circulation utilization method of a kind of complexometry crude oil decalcifying relief liquor according to claim 1, it is characterized in that, the solid-liquid separation of solution is that intermittent type standing sedimentation is separated, or carries out continuously centrifuged separation, rotary filter press or swash plate separation, or carries out multistage continuous solid-liquid separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310571914.9A CN104629791B (en) | 2013-11-13 | 2013-11-13 | A kind of circulation utilization method of complexometry crude oil decalcifying relief liquor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310571914.9A CN104629791B (en) | 2013-11-13 | 2013-11-13 | A kind of circulation utilization method of complexometry crude oil decalcifying relief liquor |
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| CN104629791A true CN104629791A (en) | 2015-05-20 |
| CN104629791B CN104629791B (en) | 2017-01-04 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865403A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气股份有限公司 | Chemical precipitation method for hydrocarbon decalcification |
| CN101336281A (en) * | 2005-12-02 | 2008-12-31 | 通用电气公司 | Method for removing calcium from crude oil |
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- 2013-11-13 CN CN201310571914.9A patent/CN104629791B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1865403A (en) * | 2005-05-20 | 2006-11-22 | 中国石油天然气股份有限公司 | Chemical precipitation method for hydrocarbon decalcification |
| CN101336281A (en) * | 2005-12-02 | 2008-12-31 | 通用电气公司 | Method for removing calcium from crude oil |
| TWI403577B (en) * | 2005-12-02 | 2013-08-01 | Gen Electric | Method for removing calcium from crude oil |
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| CN104629791B (en) | 2017-01-04 |
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