CN101428892B

CN101428892B - Treating method for waste alkali or alkaline residue

Info

Publication number: CN101428892B
Application number: CN200810239660XA
Authority: CN
Inventors: 董国良
Original assignee: Individual
Current assignee: Individual
Priority date: 2008-12-15
Filing date: 2008-12-15
Publication date: 2011-07-27
Anticipated expiration: 2028-12-15
Also published as: CN101428892A

Abstract

The invention discloses a method for treating waste alkali liquor or alkaline residue. The method uses a fluidized bed catalytic cracker to regenerate flue gas for processing and comprises the steps: mixing alkaline residue produced by gasoline refining (gasoline alkaline residue for short), alkaline residue produced by liquid gas refining (liquid gas alkaline residue for short) as well as the alkaline residue produced by other devices; introducing the mixed alkaline residue to the fluidized bed catalytic cracker for neutralizing by the regenerated flue gas; and separating oil, phenol and naphthenate sulfides from the alkaline residue. The method separates the main pollutant phenols out by using the acidic gas CO2 and SO2 in the regenerated flue gas by using the fluidized bed catalytic cracker to neutralize OH- in the alkaline residue, and adopting the separation technology, thereby realizing the effect of changing waste into valuable in industry to discharge the neutralized, separated and treated alkaline residue and waste liquid into a sewage system and achieving the aim of reducing alkaline residue leaving factory.

Description

The treatment process of a kind of waste lye or alkaline residue

Technical field

The present invention relates to a kind of oil refining, chemical environment improvement technology, relate in particular to a kind of technology of utilizing the fluidized catalytic cracker regenerated flue gas to handle alkaline residue, alkali lye.

Background technology

In the refining of petroleum and the course of processing, for the sulfide of removing in the oil product adopts alkali washing process usually, in the process of alkali cleaning, can produce the organic various alkaline residue waste liquids that contain high density sulfide and difficult degradation, the quantity discharged of its COD, sulfide and phenol, naphthenic acid is all up to the 40%-50% of refinery gross contamination emission, along with the whole society to the raising day by day of environmental requirement and to the strict control of pollutants transfer mobile requirement, how the cost-effective harmless treatment of finishing various alkaline residues has become one of environmental issue that each Petrochemical Enterprises must solve.

Various alkaline residues have very big difference because of originate different its pollutant kinds and concentration, different alkaline residues will adopt different treatment process, refinery is in the process of producing products such as motor spirit and liquefied gas, almost all adopt alkali (NaOH) method of washing to remove mercaptan and residual hydrogen sulfide, with the stability of products such as assurance gasoline and liquefied gas, thereby produce a large amount of waste soda residues.At present, the annual about thousands of tons of of alkaline residue amount that produces of each petrochemical industry company limited refinery does not wait, and mostly processing mode is to give society and goes up some processed in units, and processing costs does not wait for 1600 yuan/ton, and is not only expensive, and the environmental pollution risk is very big.Wherein contained a large amount of phenol, naphthenic acid etc., recycling cost height, in case flow into water body and soil, consequence is very serious.Particularly phenols enters biological and people's physical efficiency and protein bound, can cause possible permanent damage, is highly toxic substance.Therefore, phenol is wherein reclaimed in the harmless processing of research alkaline residue, turns waste into wealth, and eliminates environmental pollution, and is significant.

Most of alkaline residue treatment process mainly adopt sulfuric acid to carry out alkaline residue neutralization, and in this method and the efficient height, but to the equipment requirements height, because of etching problem often causes outage, also there is greater risk in secure context simultaneously, very easily causes personal injury in the operational process.Use with alkaline residue is existing at home in the flue gas, but mainly be to adopt general flue gas of heating furnace, the flue gas of general process furnace carries difficulty big, and pressure is low, seriously corroded, therefore use very inconveniently, can not extensively be promoted, and general flue gas of heating furnace negative pressure normally, even supercharging, not only consume a large amount of electric energy, also can only be pressurized to about 4KPa, conveying and use are still very difficult.

Processing for alkaline sewage, external relatively more current way is to adopt wet oxidation process, wet oxidation process can be divided into the Catalytic Wet Oxidation under air wet oxidation and the catalyzer condition, and the air wet oxidation can be divided into the High Temperature High Pressure wet oxidation again and relax wet oxidation according to operational condition.Wherein High Temperature High Pressure wet oxidation and Catalytic Wet Oxidation have only a small amount of application at home.Mitigation wet oxidation+SBR the treatment process of the Sinopec Fushun research institute exploitation that present domestic application is more, reach the purpose of improving the alkaline residue biodegradability by removal to most of sulfide in the alkaline residue, alkaline residue after the oxide treatment through the biochemical concentration that further lowers pollutent of SBR, enters oil-containing sewage treatment system at last again and carries out advanced treatment again.

Facts have proved the shortcoming that the aforesaid method processing exists: (1) High Temperature High Pressure wet-type oxidation technology usually conduct amount is not high, and one-time investment and working cost are huge, as raise about 2000 tons of the annual alkaline residue amount that produces of sub-petrochemical industry company limited refinery, processing mode is to give society to go up some processed in units, 1600 yuan/ton of processing costss, not only expensive, and the environmental pollution risk is very big.(2) relax the alkaline residue that wet oxidation+SBR technology is compared with the High Temperature High Pressure wet-type oxidation technology does not influence the diesel refining generation, the recovery and the utilization of naphthenic acid and phenol in the refining alkaline residue that produces of catalytic gasoline, but identical with it is that one-time investment and working cost are higher, by 250 yuan of/ton handlings, only this item is also up to 5,000,000/year, simultaneously owing to relax the reduction of wet oxidation operating severity, only kept the sulfide higher removal, to COD oxidation removal rate only is 20-30%, even still can increase the processing load of follow-up oil-containing sewage treatment system and the possibility that impacts up to 5000-30000 by COD behind the SBR.

Therefore, being badly in need of a kind of easy and simple to handle, investment and the lower technology of processing costs is the task of top priority.

Summary of the invention

Problem and defectives such as the equipment corrosion that exists in above-mentioned is serious in order to solve, investment and running cost height, operation easier are big, the invention provides a kind of mainly utilize the fluidized catalytic cracker regenerated flue gas handle waste lye or alkaline residue method.

The present invention adopts the fluidized catalytic cracker regenerated flue gas that alkaline residue is neutralized, with acidic gas in flue gas CO2, SO2 the NaOH in waste lye or the alkaline residue, sodium napthionate, phenol sodium, sodium sulphite etc. are converted into yellow soda ash, naphthenic acid, phenol and hydrogen sulfide etc., remove phenol, naphthenic acid, oil, sulfide, COD etc. with isolation technique then, harmless waste water is entered the existing wastewater treatment field of factory further handle.

The present invention tests by the following technical programs and realizes:

A kind of waste lye or alkaline residue processing method involved in the present invention, this method utilize the fluidized catalytic cracker regenerated flue gas to handle, and comprising: the alkali lye of gasoline refining generation or the alkali lye or the alkaline residue of alkaline residue and the refining generation of liquefied gas are in harmonious proportion; Feed regeneration fume from catalytic cracking in waste lye after mediation or the alkaline residue and carry out neutralization reaction, reduce pH value; So that further isolate oil in waste lye or the alkaline residue and phenol, naphthenic acid, sulfide etc.

The described step of utilizing the fluidized catalytic cracker regenerated flue gas to handle also comprises: impurity and salt in multistage sedimentation, centrifugation, filtering waste lye or the alkaline residue; Further extract crude phenols, naphthenic acid etc. by absorption reaction; Management is arranged being discharged into existing sewage work carries out comprehensive treating process with post-treatment aqueous phase.

Mainly comprise sour gas CO in the described fluidized catalytic cracker regenerated flue gas ₂, SO ₂And NO _x, and this sour gas with the NaOH in waste lye or the alkaline residue, phenol sodium, sodium napthionate, sodium sulphite carry out neutralization reaction be converted into yellow soda ash and phenol,, naphthenic acid, hydrogen sulfide.CO in the described fluid catalytic cracking flue gas ₂Concentration is 12-15%.The temperature of described fluid catalytic cracking flue gas is 600-700 ℃.Pressure is 0.2MPa.

Fluidized catalytic cracker regenerated flue gas among the described step B by neutralization reactor be in harmonious proportion after waste lye or alkaline residue neutralize; Described step C isolated oil and phenol, naphthenic acid etc. from waste lye or alkaline residue are to carry out centrifugation and multistage settlement separate by separating machine; Impurity in described step D waste lye or the alkaline residue is that the strainer by special use carries out filtering.

During described fluidized catalytic cracker regenerated flue gas and waste lye or alkaline residue carry out and the time temperature of reaction be 30-70 ℃, and the pressure of this fluid catalytic cracking flue gas is 0.2MPa.Facts have proved described fluidized catalytic cracker regenerated flue gas and waste lye or alkaline residue carry out in and the time temperature of reaction be preferably 50-60 ℃, pH value should be controlled at 7-9.

The beneficial effect of technical scheme provided by the invention is:

Utilize among CO2 contained in the fluidized catalytic cracker regenerated flue gas, the SO2 and the OH-in waste lye or the alkaline residue, adopt isolation technique simultaneously, separation such as principal pollutant phenols, naphthenic acid, oils, sulfide, COD are come out, turn waste into wealth, make neutralization back alkaline residue waste liquid can enter sink drainage, discharge through further handling the back, reach the alkaline residue purpose of not dispatching from the factory; Characteristics such as this project also has less investment, instant effect, operational risk is low, equipment is simple and reliable, running cost is low can make full use of resource in the factory, can realize with watershed management, with the cleaner production target of dirty pollution treatment.And reduced the content of S in the flue gas to a certain extent, played good result, for social enviroment protection has been made certain contribution with dirty pollution treatment, the treatment of wastes with processes of wastes against one another.

Description of drawings

Fig. 1 is alkaline residue of the present invention or alkali lye treatment scheme synoptic diagram;

Fig. 2 varies with temperature synoptic diagram in the alkaline residue reaction times.

Embodiment and example

For making the purpose, technical solutions and advantages of the present invention clearer, embodiment of the present invention is described further in detail below in conjunction with accompanying drawing:

As shown in Figure 1, showed the flow process to alkaline residue or alkali lye processing of the present invention, mainly comprised:

All alkaline residues are squeezed into mixing tank in proportion and add a certain proportion of water fully concoct, dilute.

Waste lye after the blending dilution or alkaline residue feed flue gas in reactor carries out counter current contact and fully reacts.

Isolate most oil and phenol, naphthenic acid etc. by multistage settling vessel, sedimentator.

By strainer filtering from liquid phase with mechanical impurity and salt.

Waste lye after neutralization separates or alkaline residue pass through adsorptive reactor further with propositions such as crude phenols, naphthenic acid.

The treatment solution that gives off is carried out comprehensive treating process.

Embodiment 1

The normal temperature neutralization test

Normal temperature experiment alkaline residue amount is 1 liter, and alkaline residue is that alkaline residue and the refining alkaline residue that produces of catalytic gasoline that liquid gas sweetening produces constituted by 4: 1.Feed gas mixture PH to 9 after 8 hours, in and pressure be normal pressure.Surveyed a pH value every two hours with the PH test paper during the neutralization, 32 stage tests are carried out in experiment respectively, and per stage needed neutralize in 16 hours,

In the normal temperature (20) and experimental data (32 times average), average test result (referring to table 1) is as follows:

Table 1

Test shows CO ₂, SO ₂Can effectively reduce the pH value of alkaline residue.

Embodiment 2

The intensification neutralization test

For investigate temperature in and the influence of speed, the alkaline residue that each elevated temperature test uses is the same with cold test, usage quantity still is 1 liter, reactor is put into the waters device carry out 25 ℃, 30 ℃, 35 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ are carried out 5 groups of constant temperature neutralization tests, feed mixing tank separately, in and pressure be normal pressure, the intensification neutralization test is carried out in test respectively 32 times, all be warmed up to 70 ℃ gradually at every turn, write down 25 ℃ respectively, 30 ℃, 35 ℃, 40 ℃, 50 ℃, 60 ℃, data in the time of 70 ℃, in the intensification and experimental data (32 times average), average test result (referring to table 2) is as follows:

Table 2

Sequence number	Project	PH	Sulfide	COD	Phenol	Oil	The used time
								1	Before the neutralization	14	1357	162960	26689	3335	0
2	After 25 ℃ of neutralizations	9.0	1243	94488	24551	345.8	8
								3	After 30 ℃ of neutralizations	9.0	1100	99933	24556	321	8
4	After 40 ℃ of neutralizations	9.0	999	83334	23303	324	7.7
								5	After 50 ℃ of neutralizations	9.0	1010	61133	23087	290	4.5
6	After 60 ℃ of neutralizations	9.2	919	50587	21045	289.4	4.0
								7	After 70 ℃ of neutralizations	9.0	853	48988	19058	256	3.7

From the reaction times, 20-40 ℃ does not have too big influence to speed of response, and with temperature increase to 50 ℃, 60 ℃, 70 ℃, speed of response obviously improves, and reaction back liquid phase oil content, phenol content, COD have part to descend.Will see that simultaneously 50-60 ℃ of speed of response improves comparatively fast, and sees that according to the use experience of petroleum chemical industry 70 ℃ of stagnation point that are alkali to equipment corrosion exceed this temperature, therefore system's seriously corroded should not improve temperature again.Be illustrated in figure 2 as the relationship change curve of alkaline residue reaction times and temperature.

In settlement separate experiment, get 60 ℃ of experiment neutralizers, it is left standstill 24 hours after, the temperature room temperature, neutralizer is divided into two-layer naturally, there is camera on skim upper strata about 6%, and analyzes lower floor's water, carries out 18 sedimentations altogether and surveys, each result is more or less the same.The settlement separate front and back of alkaline residue data contrast (18 times are average), test average result (referring to table 3) is as follows:

Table 3

Sequence number	PH	Sulfide	COD	Phenol	Oil
						60 ℃ of neutralizers separate the back water	9.0 9.0	919 633	50587 17532	21045 894	289.4 222

Centrifugation and adsorption cleaning: the analytical results from table 3, COD and other pollutent of the water (after the skim organic phase) after settlement separate are still higher, because the density of phenol is 1.04g/cm ³, neutralization back lower layer of water phase density is 1.08g/cm ³, density difference is little, adds that phenol has certain solubleness usually in water, phenol and in and the lower layer of water certain difficulty that has been separated behind the moisture, therefore also must be to removing the further purifying treatment of lower floor's water after the organic phase.Three steps are taked in purification: the first step is used earlier the whizzer centrifugation; Second step filtered solid sediment with the strainer of unique design manufacturing again; The 3rd step was carried out absorption reaction, contrasted (48 times are average) in the catalytic gasoline alkaline residue and before and after purifying, and analytical results (referring to table 4) is as follows:

Table 4

Sequence number	PH	Sulfide	COD	Phenol	Oil	Remarks
							1 2	9.0 9.0	633 566	17532 8300	894 38	222 163	After purifying before purifying

As can be seen, through after the purifying treatment, organism descends significantly, and COD also descends significantly.

Above-mentioned experimental study shows, the sour gas CO in the fluidized catalytic cracker regenerated flue gas ₂, SO ₂In can be effectively and alkaline residue, make pH value reach normal level, COD, phenol, wet goods pollutent index can be reached device sewage discharge level by technique means such as settlement separate, centrifugation and adsorption cleanings.Described reaction can be carried out promptly at normal temperatures: 30-70 ℃, but suitably improve temperature of reaction, and can accelerate neutralization reaction speed, suitable reaction temperature should be selected 50-60 ℃, the regeneration temperature basically identical of this temperature and mercaptan removal alkali; Temperature of reaction surpasses 70 ℃, and metal has the danger that caustic embrittlement takes place, should not be high again, and this is related to the selection of industrialized unit in the future and the maintenance of investment and equipment.

Embodiment 3

Since in the fluidized catalytic cracker regenerated flue gas except containing CO ₂Also have a certain amount of dust and SO outward, ₂, NO _xDeng sour gas, we mainly study the main neutralization reaction condition and the purification of neutralizer, therefore, on the basis of laboratory preliminary study, have carried out on-the-spot neutralization reaction sideline test again.

1, sideline test

Sideline test is that the high-temperature flue gas (flue gas is formed referring to table 5) that adopts the fluidized catalytic cracker revivifier to discharge carries out neutralization reaction with alkaline residue, and principal reaction is as follows:

CO ₂+2NaOH＝Na ₂CO ₃+H ₂O

Na ₂CO ₃+CO ₂+H ₂O＝2NaHCO ₃

SO ₂+2NaOH＝Na ₂SO ₃+H ₂O

Na ₂SO ₃+SO ₂+H ₂O＝2NaHSO ₃

2Na ₂S+5SO ₂+2H ₂O＝3S+4NaHSO ₃

C ₆H ₅-0-Na+CO ₂+H ₂O＝C ₆H ₅-0H+NaHCO ₃

Table 5

Reality also has the existence of many side reactions, as: the oxynitride in the flue gas, the phenols in the alkali lye, poly-phthalocyanine cobalt etc. can produce redox reaction, because main reaction----acid-base neutralisation reaction influence is not put aside very much.624 ℃ of on-the-spot flue-gas temperatures, alkaline residue are that the alkaline residue that on-the-spot alkaline residue that produces with the catalytic gasoline mercaptan removal and liquid gas sweetening produce was configured by 4: 1, and 5 liters of volumes are in order to prevent that crystallization from influencing neutralization and adding service water with 5 liters of volumes again, totally 10 liters.Neutralization reaction need not to heat again, is no more than 70 ℃ but regulate in the exhaust gas volumn basic controlling with temperature in the kettle, and pH value can reach about 9 after 10 hours, can reach 8.5 after 14 hours, mainly is the prolongation along with the time, SO ₂Not only participate in the neutralization reaction of alkali Deng acid stronger gas, the reaction later stage also with Na ₂CO ₃And NaHCO ₃Increasing sulphite is produced in reaction.Therefore, the pH value about 9 that in general neutralizes gets final product.

2, purifying treatment test

Purifying treatment analysis of experiments average result (referring to table 6) is as follows:

Contrast (32 times average) in the flue gas and after the pilot scale before and after the effluent purifying

Table 6

Classification	PH	Sulfide	COD	Phenol	Oil
						Neutralization back mixed solution	8.5	1334	40156	12142	569
The inorganic phase of settlement separate back lower floor	8.8	963	18867	973	366
						After the inorganic purification mutually	9.0	577	8334	45	169

Embodiment 4

Fluidized catalytic cracker regenerated flue gas technology and catalytic wet oxidation technology are in the contrast of reaction conditions, neutralising arrangement number of devices, consumption and staffing and effluent quality:

1, the contrast (referring to table 7) of fluidized catalytic cracker regenerated flue gas (abbreviation regenerated flue gas) neutralizing treatment alkaline residue technology and catalyzed oxidation technological reaction condition

Table 7

Condition	Temperature ℃	Pressure MPa	Neutralization medium	Vent gas treatment
					The neutralization of fluidized catalytic cracker regenerated flue gas	60	0.2	Flue gas	From compressing into incinerator
Catalyzed oxidation	200	2.2	The vitriol oil	Induced draft fan is introduced incinerator

2, in the fluidized catalytic cracker regenerated flue gas and technology and catalytic wet oxidation process unit number of devices contrast (referring to table 8)

Table 8

3, investment, consumption and staffing contrast (referring to table 9)

Table 9

4, neutralization of fluidized catalytic cracker regenerated flue gas and catalytic wet oxidation effluent quality contrast (referring to table 10)

Table 10

In sum, fluidized catalytic cracker regenerated flue gas neutralizing treatment alkaline residue is compared with the catalytic wet oxidation technology has following characteristics (1) energy consumption aspect: because the fluidized catalytic cracker regenerated flue gas itself has certain pressure, therefore device only consumes the circulation usefulness of a spot of electricity for alkaline residue in operational process, and catalytic wet oxidation will use powerful compressor that air is compressed to more than the 2Mpa.(2) facility investment aspect: catalytic wet oxidation needs sound equipment to amount to 153, and only need about 12 sound equipment with technology in the fluidized catalytic cracker regenerated flue gas, working pressure and temperature also are starkly lower than the catalytic wet oxidation method, do not need to consider the vitriolic corrosion, therefore investment will be far below the catalytic wet oxidation device in addition.(3) operation and labour cost aspect: in the fluidized catalytic cracker regenerated flue gas and technical finesse,, need not increase staffing because equipment is simple, easy to operate.And the catalytic wet oxidation device is wanted 20 operative employees.(4) effluent quality aspect: as can be seen from the data ratio, catalyzed oxidation technology effluent quality is being on close level after settlement separate with the flue gas neutralizer only also, because purifying, the laboratory is not subjected to the restriction of air speed and time, can reach higher level, it is fully passable to reach the level the same with the catalytic wet oxidation effluent quality after the industrialization.

The alkaline residue processing method that this example provides, by utilizing FCC regenerated high-temperature flue gas and wherein contained CO2, SO2, in and alkaline residue in OH-, adopt isolation technique simultaneously, separation such as principal pollutant phenol, naphthenic acid, oil, sulfide are come out, turn waste into wealth, make neutralization back alkaline residue treatment solution can enter sink drainage industrial the realization, discharge through further handling the back, reach the alkaline residue purpose of not dispatching from the factory.

The above; only be preferable embodiment and the example of the present invention; but protection scope of the present invention is not limited thereto; anyly be familiar with those skilled in the art in the technical scope that the present invention discloses; the variation that can expect easily or replacement; so long as (comprise name changing: as the catalysis flue gas with the fluidized catalytic cracker regenerated flue gas; the catalytic regeneration flue gas; the catalytic unit flue gas; the catalytic unit regenerated flue gas; the FCC flue gas; the FCC regenerated flue gas; catalytic cracking flue gas; the catalytic cracking unit flue gas; regeneration fume from catalytic cracking; the catalytic cracking unit regenerated flue gas; fluid catalytic cracking flue gas etc.) handle alkali lye; waste lye and alkaline residue etc. all belong to infringement act, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.

Claims

1. the treatment process of waste lye or alkaline residue is characterized in that described method utilizes the fluidized catalytic cracker regenerated flue gas to handle, and comprising:

A is in harmonious proportion all waste lyes or alkaline residue;

B after mediation waste lye or alkaline residue in feed the fluidized catalytic cracker regenerated flue gas and neutralize;

The fluidized catalytic cracker regenerated flue gas by neutralization reactor be in harmonious proportion after waste lye or alkaline residue neutralize;

C is by multistage settling vessel and separator, carry out sedimentation and isolate waste lye or alkaline residue in oil and phenol, naphthenic acid, sulfide;

Isolated oil and phenol, naphthenic acid, sulfide are to carry out centrifugation and multistage settlement separate by separating machine from waste lye or alkaline residue;

CO in the described fluidized catalytic cracker regenerated flue gas ₂The concentration height is 12-15%;

The temperature height of described fluidized catalytic cracker regenerated flue gas is 600-700 ℃;

And the pressure of this fluidized catalytic cracker regenerated flue gas is 0.2MPa;

During described fluidized catalytic cracker regenerated flue gas and waste lye or alkaline residue carry out and the time temperature of reaction be 50-60 ℃, the pH value is controlled at 7-9.

2. waste lye according to claim 1 or alkaline residue processing method is characterized in that, the described step of utilizing the fluidized catalytic cracker regenerated flue gas to handle also comprises:

Impurity and salt in D, filtering waste lye or the alkaline residue;

Impurity in waste lye or the alkaline residue carries out filtering by strainer;

E, extract crude phenols, naphthenic acid, sulfide and oil by absorption reaction;

F carries out comprehensive treating process with the treatment solution that gives off.

3. the treatment process of waste lye according to claim 1 or alkaline residue is characterized in that, mainly comprises sour gas CO in the described fluidized catalytic cracker regenerated flue gas ₂, SO ₂And NOx, and this sour gas neutralizes the NaOH in waste lye or the alkaline residue, sodium napthionate, sodium phenolate, sodium sulphite and is converted into yellow soda ash, naphthenic acid, phenol and hydrogen sulfide.