CN109337710A

CN109337710A - A kind of liquid antichlor

Info

Publication number: CN109337710A
Application number: CN201811136641.4A
Authority: CN
Inventors: 蒋旭辉
Original assignee: Individual
Current assignee: Individual
Priority date: 2018-09-28
Filing date: 2018-09-28
Publication date: 2019-02-15

Abstract

The invention discloses a kind of liquid antichlors, including phase transfer catalyst, organic amine, hydrophilic organic solvent and water.By volume, the ratio of the phase transfer catalyst, organic amine, hydrophilic organic solvent and water is respectively 5~2:2~1:2.5~1:2.5~1.A kind of liquid antichlor of the invention, the injection of the agent can significantly reduce the content of organic chloride after electro-desalting in crude oil, HCL is effectively reduced to the corrosivity of each device overhead condensation pipeline, the safe operation of oil refining apparatus has farthest been ensured, has improved refinery economics benefit.

Description

A kind of liquid antichlor

Technical field

The present invention relates to a kind of liquid antichlors, belong to crude oil except chlorine reagent field.

Background technique

As oil field two is adopted, three in poor quality for adopting crude oil, butter, organic chloride content in crude oil gradually increase Greatly, the presence of these chlorides threatens the safety in production of atmospheric and vacuum distillation unit, while chloride ion is for austenite stainless steel The equipment and pipeline of matter are also easy to produce pitting and stress corrosion, it is also possible to the problems such as causing catalyst contamination, poisoning, therefore chloride Larger harm can be generated to secondary operation device, this has not only seriously affected the long period safe operation of oil refining process units, It will cause great economic loss.Existing liquid antichlor is by carrying out nucleophilic substitution with the organic chloride in oily phase Remove the organochlorine in crude oil, but existing antichlor is not easy to contact in dechlorination process with organochlorine, there are organochlorines The lower disadvantage of removal efficiency.

Summary of the invention

The technical problem to be solved by the present invention is to overcome above-mentioned problem, providing a kind of antichlor can be with having in crude oil Machine chlorine comes into full contact with, has the advantages that selectivity is good, dechlorination condition is simple, HCl content is high, after capable of can significantly reduce electro-desalting The liquid antichlor of content of organic chloride in crude oil.

In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:

A kind of liquid antichlor, including phase transfer catalyst, organic amine, hydrophilic organic solvent and water.

By volume, the ratio of the phase transfer catalyst, organic amine, hydrophilic organic solvent and water is respectively 5~2:2 ~1:2.5~1:2.5~1.

The phase transfer catalyst includes one in benzyltriethylammonium hydroxide, tetrabutylammonium hydroxide and polyethylene glycol Kind or several mixtures.

The organic amine is ethylenediamine.

The hydrophilic organic solvent is alcohol organic solvent.

The water includes deionized water or distilled water.

The phase transfer catalyst, organic amine, hydrophilic organic solvent and water ratio be 5:2:2.5:2.5.

The phase transfer catalyst, organic amine, hydrophilic organic solvent and water ratio be 2:1:1:1.

Beneficial effects of the present invention: a kind of liquid antichlor provided by the invention, the mixture being grouped as by multiple groups, it is not Excellent, the de- organochlorine effect of metal ion, good water solubility, chemical stability is good, and rises with the demulsifier that original is added and cooperate with effect It answers, does not influence the effect of demulsifier, in addition, the agent varies without any technique, directly at electric desalting apparatus filling decalcifying agent Injection, has the characteristics that easy to operate.

Specific embodiment

The present invention will be further described below with reference to examples, and following embodiment is only used for clearly illustrating this hair Bright technical solution, and not intended to limit the protection scope of the present invention.

Specific embodiment 1

By volume, the ratio of the phase transfer catalyst, organic amine, hydrophilic organic solvent and water is respectively 5~2:2 ~1:2.5~1:2.5~1, preferably 5:2:2.5:2.5.

The phase transfer catalyst includes one in benzyltriethylammonium hydroxide, tetrabutylammonium hydroxide and polyethylene glycol Kind or several mixtures, preferably benzyltriethylammonium hydroxide.

The organic amine is ethylenediamine.

The hydrophilic organic solvent is alcohol organic solvent, preferably ethyl alcohol.

The water includes deionized water or distilled water, preferably deionized water.

Specific embodiment 2

By volume, the ratio of the phase transfer catalyst, organic amine, hydrophilic organic solvent and water is respectively 5~2:2 ~1:2.5~1:2.5~1, preferably 3.5:1.5:1.8:1.8.

The phase transfer catalyst includes one in benzyltriethylammonium hydroxide, tetrabutylammonium hydroxide and polyethylene glycol Kind or several mixtures, preferably tetrabutylammonium hydroxide.

The organic amine is ethylenediamine.

The hydrophilic organic solvent is alcohol organic solvent, preferably methanol.

Specific embodiment 3

By volume, the ratio of the phase transfer catalyst, organic amine, hydrophilic organic solvent and water is respectively 5~2:2 ~1:2.5~1:2.5~1, preferably 2:1:1:1.

The phase transfer catalyst includes one in benzyltriethylammonium hydroxide, tetrabutylammonium hydroxide and polyethylene glycol Kind or several mixtures, preferably polyethylene glycol (molecular weight 200~600).

The organic amine is ethylenediamine.

The water includes deionized water or distilled water, preferably ionized water.

For the liquid antichlor obtained in the specific embodiment 1, wherein phase transfer catalyst, organic amine, hydrophily have Solvent and the volume of water choose 250mL, 100mL, 150mL and 150mL respectively.By the dechlorination of 300mL feedstock oil and proportional quantity The water of agent and proportional quantity, proportional quantity oil-soluble demulsifier be added three-necked flask in, load onto thermometer, stirring rod, condenser pipe return Stream, heat temperature raising control are reacted 1 hour between 80~95 DEG C, separatory funnel are transferred to after cooling, under static layering removal Layer water, taking upper oil phase using the detection of microcoulomb instrument, wherein chlorinity, test result are as shown in table 1.

1# oil sample is 300ml+300ml distilled water (blank control adds dosage 0%)

2# oil sample is 300ml+300ml distilled water+1.5ml antichlor (adding dosage 0.5%)

3# oil sample is 300ml+300ml distilled water+0.3ml antichlor (adding dosage 0.1%)

4# oil sample is 300ml+200ml distilled water+0.3ml antichlor (adding dosage 0.1%).

The experiment parameter of each sample is as it appears from the above, test result is as shown in table 1.

Sample number into spectrum	Chlorinity ppm	Dechlorination rate %	Remarks
				1#	54.010		Not plus antichlor
2#	12.431	77%	0.5%
				3#	13.840	74.3%	0.1%
4#	11.137	79.4%	0.1%

Table 1

From table 1 it follows that the injection of liquid antichlor can significantly reduce the content of organic chloride after electro-desalting in crude oil, Removal efficiency is more than 70%, can be effectively reduced HCL to the corrosivity of each device overhead condensation pipeline, farthest ensures The safe operation of oil refining apparatus improves refinery economics benefit.

In addition, contrast sample 3# and 4#, antichlor concentration improves half, and when adding dosage identical, dechlorination rate is substantially close to dense When degree improves, dechlorination rate can not be multiplied, and there are effect differences for the possible laboratory water-oil separating of reason, cause a part de- Chlorine afterwards is present in Water-In-Oil, static obvious during the test it can be seen that the water of bottom will less very compared to the water being added It is more.

Organic chloralkane in crude oil, vegetable and animals oils can be reacted with the organic amine of strong basicity generate organic chloride ammonium and Fatty alcohol, fatty alcohol is soluble in oily phase and stays in crude oil or vegetable and animals oils, and organic chloride ammonium is soluble in water as electricity is de- Salt device water-oil separating is removed together, but this process does not have under phase transfer catalyst participation, reaction speed and its slow Slowly, therefore liquid antichlor has carried out being alkylated instead between grease phase using the catalytic action of the phase transfer catalyst of oil-containing It answers.The reaction mechanism is as follows for it (being citing with benzyltriethylammonium hydroxide):

Cation exchange

C₁₃H₂₂N⁺OH^-+R⁺CL^-=R⁺OH^-+C₁₃H₂₂N⁺CL^-(oily phase) (1)

Phase transfer: C₁₃H₂₂N⁺CL^-(oily phase)=C₁₃H₂₂N⁺CL^-(water phase) (2)

Anion exchange:

2C₁₃H₂₂N⁺CL^-+H₂NCH₂CH₂NH₂+2H₂O=

2C₁₃H₂₂N⁺OH^-+CLH₃NCH₂CH₂NH₃CL (water phase) (3)

Phase transfer: C₁₃H₂₂N⁺OH^-(water phase)=C₁₃H₂₂N⁺OH^-(oily phase) (4)

Firstly, nucleophilic substitution occurs for the chloride in phase transfer catalyst benzyltriethylammonium hydroxide and crude oil, Fatty alcohol and benzyltriethylammoinium chloride are generated, chlorine is mutually transferred to water phase from oil.Second step, benzyltriethylammoinium chloride and second two Amine reaction generation second dichloride ammonium salt is dissolved in water and is removed with electro-desalting water-oil separating, meanwhile, benzyltriethylammoinium chloride quilt It is reduced into phase transfer catalyst benzyltriethylammonium hydroxide.Consisting of phase-transferring agent catalyst is in the above process with benzyl triethyl ammonium chlorination Two kinds of forms of ammonium and benzyltriethylammonium hydroxide constantly recycle between water-oil phase, keep organic chloride favourable conversions solvable Property ammonium chloride is removed with water.

In order to verify influence of the demulsifier to antichlor of the invention, following sample, test method and front are made It is identical.

Sample 5# is oil sample 300ml+300ml distilled water+0.3ml antichlor (adding dosage 0.1%)+demulsifier 0.3ml.

Sample 6#: take the supernatant liquid 90ml obtained after sample 5# dechlorination that 0.3ml demulsifier is added to add distilled water 40ml again Left and right cold stirring a few minutes, the as secondary demulsification of secondary washing, water-oil separating is relatively clear, but oil sample wadding is flower-shaped, and the time puts Still there is clean water precipitation after length.

Sample 7#: oil sample 300ml+300ml distilled water+0.3ml antichlor (adding dosage 0.1%)

Sample 8#: take the supernatant liquid 100ml obtained after sample 7# oil sample dechlorination that 0.3ml demulsifier is added to add distillation again Water 100ml or so cold stirring a few minutes, as secondary washing are once demulsified, and water-oil separating is relatively clear, and supernatant liquid is in black.

Test result is as shown in table 2, and antichlor and demulsifier have synergistic effect as can be seen from the table, and demulsifier is to dechlorination Water-oil separating has effect, especially secondary be demulsified to facilitate the raising of dechlorination rate afterwards.

Table 2

A kind of liquid antichlor of the invention, is mainly used in refinery, oil field, vegetable oil add the desalination system of hydrogen, in electricity De- is under the conditions of filling the water under operating condition, infuse demulsifier and sufficiently mix etc., which can effectively remove the organochlorine in crude oil, It is removed with sedimentation separation water process, dechlorination rate is generally between 50~95%.

The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered It is considered as protection scope of the present invention.

Claims

1. a kind of liquid antichlor, it is characterised in that: including phase transfer catalyst, organic amine, hydrophilic organic solvent and water.

2. a kind of liquid antichlor according to claim 1, it is characterised in that: by volume, the phase transfer catalyst, The ratio of organic amine, hydrophilic organic solvent and water is respectively 5~2:2~1:2.5~1:2.5~1.

3. a kind of liquid antichlor according to claim 1 or 2, it is characterised in that: the phase transfer catalyst includes benzyl One of base triethylammonium hydroxide, tetrabutylammonium hydroxide and polyethylene glycol or several mixtures.

4. a kind of liquid antichlor according to claim 1 or 2, it is characterised in that: the organic amine is ethylenediamine.

5. a kind of liquid antichlor according to claim 1 or 2, it is characterised in that: the hydrophilic organic solvent is alcohol Class organic solvent.

6. a kind of liquid antichlor according to claim 1 or 2, it is characterised in that: the water include deionized water or Distilled water.

7. a kind of liquid antichlor according to claim 2, it is characterised in that: the phase transfer catalyst, organic amine, parent Aqueous organic solvent and the ratio of water are 5:2:2.5:2.5.

8. a kind of liquid antichlor according to claim 2, it is characterised in that: the phase transfer catalyst, organic amine, parent Aqueous organic solvent and the ratio of water are 2:1:1:1.