CN104449811B

CN104449811B - A kind of Demetalization method by hydrocarbon oil

Info

Publication number: CN104449811B
Application number: CN201310433738.2A
Authority: CN
Inventors: 于丽; 沈明欢; 王振宇
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2013-09-23
Filing date: 2013-09-23
Publication date: 2016-03-02
Anticipated expiration: 2033-09-23
Also published as: CN104449811A

Abstract

The present invention relates to a kind of Demetalization method by hydrocarbon oil, comprising: the ester of hydrocarbon ils and aliphatic dibasic acid, water and emulsion splitter are mixed, then carries out oily water separation; Acid number >=the 0.5mgKOH/g of described hydrocarbon ils.Process for demetalizating of the present invention can in crude oil desalting process by the most of metal transfer in crude oil in aqueous phase, and adverse influence can not be produced to electric desalting apparatus.

Description

A kind of Demetalization method by hydrocarbon oil

Technical field

The present invention relates to a kind of Demetalization method by hydrocarbon oil, particularly a kind of method of hydrocarbon oil decalcifying.

Background technology

In recent years along with the increase of crude oil with poor quality ratio in extraction crude oil, the content of metal in crude oil, particularly some alkaline-earth metal such as Ca content increases greatly, and they are processed on crude oil the impact brought and are day by day subject to people's attention.Research shows, in stock oil, Ca content increases, and significantly will reduce catalyst molecule sieve and substrate area, and directly affect the activity of catalyzer.In recent years there is the phenomenon of catalytic cracking catalyst poisoning and deactivation in the refinery of some refining high calcium-containing crude oil, not only makes yield of light oil significantly reduce, but also have influence on downstream residual oil quality, causes the crude oil of refinery to process profit and greatly reduce.

Calcium in crude oil, small part exists with water-soluble salt, slightly soluble salt such as the forms such as calcium chloride, Calcium hydrogen carbonate, calcium sulfate, calcium carbonate, and major part exists with oil soluble petroleum acid calcium.In the electric desalting process of general refinery, mainly remove most inorganic salt, almost removal effect is not had to the petroleum acid calcium of organic bound state.This part metal overwhelming majority remains in vacuum residuum, have impact on the further processing to vacuum residuum and utilization.

Relevant crude oil demetalization technology, has carried out more research work both at home and abroad.Three major types can be roughly divided into industrial widely used decalcifying agent according to its mechanism of action: (1) precipitation agent disclosed in current domestic and foreign literature, mainly can generate polyphosphoric acid and its esters of hydrophilic slightly soluble or indissoluble salt, phosphoric acid, carbonic acid, sulfuric acid, silicic acid or its esters with calcium in oil.Due to generate calcium carbonate, calcium sulfate or calcium phosphate slightly soluble or water insoluble, and easily carried secretly by oil phase and thus make the decalcification effect of such metal remover be affected, as CN1611569A, CN1611570A, CN1760338A.(2) mineral acid, mainly can generate the hydrochloric acid, nitric acid etc. of water soluble salt, as CN1431276A with Ca.(3) organic acid, mainly monocarboxylic acid, di-carboxylic acid, aminocarboxylic acid, organic phospho acid, organic sulfonic acid, organic phosphine sulfonic etc., as CN1454967A.In all these metal removers, mainly refer to acidizer and some salts.

Current crude oil demetalization is decalcification successful Application on industrial electro desalting plant mainly, although acidizer metal removal effect is obvious viewed from the result of application at present, but because its acidity is stronger, there is serious etching problem, particularly comparatively strong to the corrodibility of injecting and waterflood system, need to change injectant pump and injecting pipe material; Although some salt metal removers do not exist etching problem, metal removal effect is poor, and due to its electroconductibility comparatively strong, direct result will cause electric desalting apparatus electric current excessive, and power transmission difficulty, affects the desalting and dewatering effect of Crude Desalting System.

Summary of the invention

The present invention aims to provide a kind of Demetalization method by hydrocarbon oil, most of metal (particularly calcium) in crude oil can (in particularly electric desalting process) be transferred in aqueous phase by this process for demetalizating in crude oil desalting process, can not produce adverse influence to electric desalting apparatus.Hydrocarbon ils, after the method process, greatly can reduce the content of wherein metal especially calcium, thus improve the quality of catalytic cracking and hydrocracking hydrocarbon feed.

A kind of demetallated method of hydrocarbon ils, comprising: the ester of hydrocarbon ils and aliphatic dibasic acid, water and emulsion splitter are mixed, then carry out oily water separation; Acid number >=the 0.5mgKOH/g of described hydrocarbon ils.

Described aliphatic dibasic acid can be one or more in oxalic acid, propanedioic acid, succinic acid, hexanodioic acid, pimelic acid, nonane diacid and sebacic acid.

Should be understood that, the consumption of metal remover is relevant with several factors, comprise hydrocarbon oil properties, the metal concentration in hydrocarbon ils, injection rate, mixture strength, demetalization temperature, emulsion splitter dosage, oily water separation time etc., how to determine that these operating parameterss belong to prior art, after determining these operating parameterss, those skilled in the art can determine this univariate parameter of ester of aliphatic dibasic acid easily.

Hydrocarbon ils described in the present invention refers to any any hydrocarbon ils of metal such as calcium containing exceeding allowance, comprises crude oil, long residuum, vacuum residuum, diasphaltene wet goods.

Should be understood that, hydrocarbon ils is particularly in crude oil, and the alkaline-earth metal mainly contained is calcium, and these calcium major parts exist with the form of oil-soluble petroleum acid calcium.The present invention is specially adapted to the calcium removed in hydrocarbon ils, and calcium contents is higher, and the present invention more has superiority.Calcium contents >=20 μ the g/g of the preferred hydrocarbon ils of the present invention, more preferably >=100 μ g/g, further preferably >=200 μ g/g.Acid number >=the 1mgKOH/g of the preferred hydrocarbon ils of the present invention, more preferably >=2mgKOH/g, further preferably >=5mgKOH/g.Generally speaking, ensure the decalcification effect of hydrocarbon ils, the consumption of metal remover at least will reach and carry out stoichiometric calculated value by the calcium contents of hydrocarbon ils, usually to carry out stoichiometric calculated value by the calcium contents of hydrocarbon ils high by 20% ~ 200% for its amount ratio, generally its amount ratio by calcium contents carry out stoichiometric calculated value high 25% ~ 100% time can reach preferably decalcification effect.

Injection water quality is determined because of situation, know with those skilled in the art know that and how to select water quality and the water yield, as laboratory, use distilled water, full scale plant generally uses desulfurized purified water, water injection rate is generally 1% ~ 50% of hydrocarbon ils quality, and preferably water injection rate is 5% ~ 20% of hydrocarbon ils quality.

The present invention has no particular limits emulsion splitter, can select the emulsion splitter that this area routine uses.These emulsion splitters can be single emulsion splitter or composite demulsifying agent, as DE2040, FC9301, NS-9906, SP169 etc.With hydrocarbon ils quality for benchmark, the consumption of emulsion splitter is generally 1 ~ 100 μ g/g, preferably 10 ~ 50 μ g/g.

Described mixing is carried out in mixing tank, any equipment mixing process all used in the present invention mixed for immiscible liquid-liquid diphase, as on-line mixing device, mixing valve, mixing tank, agitator, homogenizer, counter-current extraction, mulser, laboratory blender etc.

Described mixing, temperature is generally 25 ~ 200 DEG C, is preferably 80 ~ 140 DEG C; Time is generally 1s ~ 24h, preferred 1min ~ 2h, more preferably 0.5 ~ 1.5h.

Time needed for oily water separation determined with separating device, temperature and hydrocarbon oil properties by mixing, and when water solution of oil is stablized, the time that breakdown of emulsion is separated with water-oil phase will be longer than the time of easy breakdown of emulsion; Similarly, the time required when temperature height is just lacked relatively, and the general time is 1s ~ 24h, preferred 1min ~ 2h, and these are all well-known to those skilled in the art.

The temperature of oily water separation is determined by hydrocarbon oil properties, density is larger, viscosity is higher, required temperature is higher, otherwise then can carry out being low to moderate under room temperature, under the condition of usual pressure, the temperature of oily water separation is below the boiling point of water, under the condition having certain pressure, suitably can improve preheating temperature and oily water separation temperature, typical temperature is at 25 ~ 200 DEG C, and preferably 80 ~ 140 DEG C, these are also all well-known to those skilled in the art.

The various scopes that this specification sheets is mentioned include their end points interior, unless expressly stated otherwise.In addition, when providing scope, one or more preferable range or a lot of preferred upper limit value and preferred lower limit value to amount, concentration or other value or parameter, it should be interpreted as specifically discloses by any all scopes formed any range higher limit or preferred value and any range lower value or preferred value, no matter whether separately disclose these numerical value pair.

Will be separated into the oil phase decreasing metal and the aqueous phase being enriched metal after profit fully mixes, the separation method of profit comprises centrifugal, standing sedimentation, added electric field, adds emulsion splitter etc.Those skilled in the art know the process of carrying out oily water separation with extra electric field, as electric desalting process conventional in hydrocarbon ils particularly crude oil upgrading process.

Adopt process for demetalizating of the present invention, not only there is good metal removal effect, particularly decalcification effect, greatly improve the quality of hydrocarbon feed, to subsequent catalyst cracking and hydrocracking process very favourable.The more important thing is, the present invention can solve current sour metal remover to the etching problem of equipment.

Embodiment

Embodiment 1

Test hydrocarbon ils is Doba crude oil, takes from Qingdao petrochemical industry, and its character is in table 1, and what its metal content was the highest is calcium, up to 235 μ g/g.Select different diesters to carry out decalcification test as metal remover respectively, the performance of each metal remover represents with decalcification rate, in order to the decalcification effect of more different metal remover, gets identical metal remover dosage 1450 μ g/g.The better test conditions that can reach according to laboratory is tested, specific as follows: electric desalting temperature 95 DEG C, high pressure 2500v, fuel oil preheating temperature about 110 ~ 120 DEG C, emulsion splitter FC-9301(is purchased from Shandong auxiliary agent company of Bin Hua group) dosage 50 μ g/g, injection rate counts 10% with crude quality.Get the stock oil being quantitatively preheated to certain temperature, by certain metal remover dosage, emulsion splitter dosage and injection rate, metal remover, emulsion splitter and distilled water and stock oil mix and blend at 90 DEG C are reacted 1h, oil-water mixture is transferred in taper electric desalting pipe, at certain temperature and current field condition, electric desalting breakdown of emulsion divides water, and the oil sample got after profit layering is made icp analysis calcium contents and calculated decalcification rate.The decalcification effect of each metal remover is in table 2.

Table 1

Project name	Analytical data
		Density (20 DEG C), g/cm ³	0.9228
Viscosity (50 DEG C), mm ²/s	143.4
		Viscosity (80 DEG C), mm ²/s	40.76
Moisture, m%	Vestige
		Lightning (opening), DEG C	109
Condensation point, DEG C	-7
		Carbon residue (Kang Shi), m%	5.28
Ash content, %	0.087
		Colloid, m%	13.5
Bituminous matter, m%	＜0.1
		Acid number, mgKOH/g	5.10
S，m%	0.14
		N，m%	0.19
Salts contg, mgNaCl/L	7
		C，m%	87.19
H，m%	12.31
		Metal content, μ g/g
Ca	235
		Fe	12.8
Mg	1.9
		Mn	7.2
Na	2.9
		Ni	12.0
V	4.8

Table 2

Different metal remover	Calcium contents (μ g/g) after de-	Decalcification rate (%)
			Diethyl oxalate	14.1	94.0
Diethyl malonate	15.9	93.2
			Diethyl succinate	17.7	92.5
Ethyl glutarate	19.5	91.7
			Diethylene adipate	20.5	91.3
Pimelic acid diethyl ester	21.4	90.9
			Ethylazelaate	23.1	90.2

Comparative example

Test crude oil is bony crude oil, its main character is in table 3, acid value for crude oil is very low, only has 0.18mgKOH/g, calcium contents is also very low, only has 0.6 μ g/g, because the existing forms of Calcium in Crude Oil is mainly calcium naphthenate, therefore in bony crude oil, add calcium naphthenate, make its calcium contents reach 235 μ g/g, then add diethyl oxalate and do decalcifying agent, decalcifying agent dosage 1450 μ g/g, adopt the condition identical with embodiment 1 and method decalcification, after de-, calcium contents is 224 μ g/g, and decalcification rate only has 4.7%.

Table 3

Embodiment 2

Test hydrocarbon ils is prince wife Cao pasture crude oil, and its essential property is in table 4.Do metal remover with diethyl oxalate, investigate the decalcification effect of the different dosage of metal remover.Test conditions is as follows: electric desalting temperature 90 DEG C, high pressure 3000v, fuel oil preheating temperature about 120 DEG C, and emulsion splitter DE2040(is purchased from Shandong auxiliary agent company of Bin Hua group) dosage 40 μ g/g, injection rate 8%.Test method is identical with embodiment 1.Test-results is in table 5.

Table 4

Project name	Analytical data	Method standard
			Density (20 DEG C)/(g/cm ³)	0.9283	GB/T2540
Viscosity (50 DEG C)/(mm ²/s)	69.53	GB/T11137
			Colloid/%	14.6	Fractionation by adsorption
Bituminous matter/%	0.8	Fractionation by adsorption
			Salts contg/(mgNaCl/L)	35	SY/T0536-94
Moisture/%	1.80	GB/T8929
			Total acid value/(mgKOH/g)	2.71	GB/T7304
Ca massfraction/(μ g/g)	148	RIPP124-90
			Fe massfraction/(μ g/g)	16.5	RIPP124-90
Na massfraction/(μ g/g)	41.7	RIPP124-90
			Ni massfraction/(μ g/g)	11.6	RIPP124-90
V massfraction/(μ g/g)	0.5	RIPP124-90
			Mg massfraction/(μ g/g)	5.7	RIPP124-90

Table 5

Decalcifying agent dosage/(μ g/g)	Calcium massfraction/(μ g/g) after de-	Decalcification rate/%
			540	53.9	63.9
600	30.2	79.6
			680	15.8	89.3
750	12.0	91.9
			850	10.8	92.7
1080	7.6	94.9

Embodiment 3

Test hydrocarbon ils is Crude Oil In Dagang, and its main character, in table 6, does metal remover with dimethyl malonate, has investigated the decalcification effect of the different dosage of metal remover.Test conditions is as follows: electric desalting temperature 90 DEG C, high pressure 2500v, fuel oil preheating temperature about 100 DEG C, and de-emulsifier SP 169(is purchased from Shandong auxiliary agent company of Bin Hua group) dosage 40 μ g/g, acetic acid catalyst dosage is 12 μ g/g, injection rate 10%.Test method is identical with embodiment 1.Test-results is in table 7.

Table 6

Project name	Analytical data	Method standard
			Density (20 DEG C)/(g/cm ³)	0.9014	GB/T2540
Viscosity (50 DEG C)/(mm ²/s)	71.95	GB/T11137
			Colloid/%	15.7	Fractionation by adsorption
Bituminous matter/%	0.1	Fractionation by adsorption
			Salts contg/(mgNaCl/L)	4.5	SY/T0536-94
Moisture/%	Nothing	GB/T8929
			Total acid value/(mgKOH/g)	0.99	GB/T7304
Ca massfraction/(μ g/g)	23.3	RIPP124-90
			Fe massfraction/(μ g/g)	7.0	RIPP124-90
Na massfraction/(μ g/g)	1.9	RIPP124-90
			Ni massfraction/(μ g/g)	33	RIPP124-90

Table 7

Metal remover dosage/(μ g/g)	Calcium massfraction/(μ g/g) after de-	Decalcification rate/%
			0	19.9	14.4
95	4.6	80.1
			115	3.3	85.7
150	1.7	92.9

Embodiment 4

Evaluate the corrodibility of different metal remover with reference to " rotary hanging plate weight-loss method " in " water coolant analysis and test method " book, test conditions is as follows: test temperature 30 DEG C, speed of rotation 75 revs/min, test period 24h.Test piece: material No. 20 highquality carbon steels, size 50.0 × 25.0 × 2.0mm, surface-area 28cm ².Choose several conventional metal remover, be made into the aqueous solution that mass concentration is 1%, investigate its corrodibility, the results are shown in Table 8, the corrodibility of ester class metal remover is minimum.With same metal remover, get identical dosage 1450 μ g/g, test method is with embodiment 1, test oil is Doba crude oil, and character is in table 1, and other test conditions is as follows: electric desalting temperature 95 DEG C, high pressure 2500v, about fuel oil preheating temperature 110-120 DEG C, emulsion splitter FC-9301(is purchased from Shandong auxiliary agent company of Bin Hua group) dosage 50 μ g/g, injection rate 10%.The results are shown in Table 9.As can be seen from the results, the metal removal effect of ester class metal remover and strong acid class metal remover is substantially suitable, but its corrodibility is very little, and the result of balance metal removal effect and erosion rate, according to different field conditions, can choose dissimilar metal remover.

Table 8

Metal remover	Corrosion speed (mm/a)
		Monocarboxylic acid	4.63
Aminocarboxylic acids	2.23
		Hydroxycarboxylic acid	2.87
Organic phosphine acids	14.49
		Ester class	0.94

Table 9

Dissimilar decalcifying agent	Calcium contents (μ g/g) after de-	Decalcification rate (%)
			Monocarboxylic acid class	4.6	98.0
Di-carboxylic acid class	13.1	94.4
			Aminocarboxylic acids	5.9	97.5
Hydroxycarboxylic acid	4.1	98.3
			Organic phosphine acids	4.1	98.3
Strong acid class	4.2	98.2
			Precipitation agent	25.3	89.2
Ester class	14.1	94.0

Claims

1. the demetallated method of hydrocarbon ils, comprising: the ester of hydrocarbon ils and aliphatic dibasic acid, water and emulsion splitter are mixed, then carry out oily water separation; Acid number >=the 0.5mgKOH/g of described hydrocarbon ils; Described aliphatic dibasic acid is several in oxalic acid, propanedioic acid, succinic acid, hexanodioic acid, pimelic acid, nonane diacid and sebacic acid, or the one in propanedioic acid, succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, nonane diacid and sebacic acid.

2. in accordance with the method for claim 1, it is characterized in that, the calcium contents >=20 μ g/g of hydrocarbon ils.

3. in accordance with the method for claim 2, it is characterized in that, the calcium contents >=100 μ g/g of hydrocarbon ils.

4. in accordance with the method for claim 1, it is characterized in that, the acid number >=1mgKOH/g of hydrocarbon ils.

5. in accordance with the method for claim 1, it is characterized in that, the water yield is 1% ~ 50% of hydrocarbon ils quality.

6. in accordance with the method for claim 1, it is characterized in that, hydrocarbon ils quality is benchmark, and the consumption of emulsion splitter is 1 ~ 100 μ g/g.

7. in accordance with the method for claim 1, it is characterized in that, mixing time is 1s ~ 24h.

8. in accordance with the method for claim 1, it is characterized in that, mixing temperature is 25 ~ 200 DEG C.

9. in accordance with the method for claim 1, it is characterized in that, described hydrocarbon ils is crude oil, long residuum, vacuum residuum or deasphalted oil.

10. according to the method described in Claims 2 or 3, it is characterized in that, it is high by 20% ~ 200% that the amount ratio of the ester of aliphatic dibasic acid carries out stoichiometric calculated value by hydrocarbon ils calcium contents.

11. in accordance with the method for claim 1, it is characterized in that, adopts electric desalting process to carry out oily water separation.