CN1056098C

CN1056098C - Method for comprehensive utilization of waste catalyst in fluidized bed furancarbinol production

Info

Publication number: CN1056098C
Application number: CN95110536A
Authority: CN
Inventors: 吴杰; 王绍松
Original assignee: Individual
Current assignee: Individual
Priority date: 1995-07-10
Filing date: 1995-07-10
Publication date: 2000-09-06
Anticipated expiration: 2015-07-10
Also published as: CN1144717A

Abstract

Furfuralcohol in discarded catalysts in the furfuralcohol production of a fluidized bed is recovered by a dry distillation method; high-temperature oxidation processing is carried out to residue after dry distillation; firstly, copper salt is extracted; then, chromium oxide is used for producing dichromate by an alkaline hydrolysis method on one hand and used for producing refining chrome green on the other hand. The discarded catalysts are fully utilized by the present invention, and products of the furfuralcohol, copper sulfate, cupric nitrate, sodium dichromate dihydrate, potassium dichromate, sodium sulfate, sodium acetate trihydrate, chrome green, etc. conforming to an industrial standard can be obtained. No waste slag is discharged; not only is the environment protected, but also high economic benefit is produced.

Description

The method of comprehensive utilization of dead catalyst during the fluid bed furfuryl alcohol is produced

The present invention relates to the comprehensive utilization of dead catalyst in a kind of fluid bed furfuryl alcohol production.

Discarded catalyst during the fluidized bed process furfuryl alcohol is produced, because the adsorptivity of catalyst, its main component is furfuryl alcohol (content about about 30%), furfural, cupric oxide (content is 26～30%), chromium oxide (content about about 35%), water etc.Generally it is acted as a fuel and burn, not only cause environmental pollution, also be a kind of wasting of resources simultaneously, once there was cupric oxide wherein to change the introduction that copper sulphate reclaims application into, but still do not obtain all utilizing fully, if these compositions are extracted or be converted into the useful industrial product, its economic benefit and social benefit will be very significant.

Purpose of the present invention is exactly to provide a kind of comprehensive utilization method to the discarded catalyst in the production of fluidized bed process furfuryl alcohol, reclaims furfuryl alcohol, and other composition mainly is converted into the useful industrial product.

Main technical schemes of the present invention is earlier dead catalyst to be carried out destructive distillation, and the method by destructive distillation reclaims furfuryl alcohol, and then other composition is utilized.

The crude product furfuryl alcohol that destructive distillation directly obtains, purity can reach more than 90%, and then further improves its purity by the method for rectifying, can reach more than 98%.

Residue behind the recovery furfuryl alcohol mainly is to carry out high temperature oxidation process, make remaining organic carbon, the further oxidation of cupric oxide, chrome green passivation (making it not to be soluble in the acid), transform the quality behind the salify with raising cupric oxide, chrome green, through after the above-mentioned high temperature oxidation process, extract mantoquita earlier, then to remaining Cr ₂O ₃The one, produce bichromate by the alkaline hydrolysis method, the 2nd, produce refining chrome green.

Describe in detail below in conjunction with accompanying drawing.

Fig. 1 is a process flow diagram of the present invention.

Fig. 2 is employed a kind of agitator structure schematic diagram in the technology of the present invention.

Among the figure: 1 dead catalyst, 2 solvents, 3 blending tanks, 4 destructive distillation jars, 5 filters, 6 rectifying jars, 7 refining furfuryl alcohol finished products, 8 residues, 9 leaching grooves, 10 filters, 11 concentration tanks, 12 crystallization tanks, 13 mother liquors, 14 centrifuges, 15 mantoquitas, 16 filter residues, 17 cosolvents, 18 roasters, 19 leaching grooves, 20H ₂O, 21 filters, 22 acid, 23 concentration tanks, 24 crystallization tanks, 25 sodium sulphate or sodium acetate, 26 filters, 27 bichromates, 28O ₂, 29 oxidation furnaces, 30 chrome green, 31 baiting valves, 32,39 stirring arms, 33 explosion stacks, 34 electric machine controllers, 35 motors, 36 worm reduction gears, 37 stuffing boxes, 38 shafts, 40 chucks.

Dead catalyst is paste, and be added in the blending tank 3 with low boiling point solvent 2 earlier and dilute, Low boiling point solvent 2 can adopt water-furfuryl alcohol solvent, can suction do to be diluted to dead catalyst Heat up in a steamer tank 4 and get final product, destructive distillation is adopted and is stirred and the high-temperature pressure-reduction condition, uses heat-conducting oil heating, and oily temperature is 250～350 ℃, the most suitable when pressure is 0.07～0.09MPa, if be lower than this temperature, Yield can reduce, and the production cycle is long, and embodiment provides in the different temperatures situation behind the specification Contrast. Reclaim crude furfuryl alcohol, content reaches more than 90%, and as further refining, crude furfuryl alcohol steams It is refining that filter 5 more than 60 orders, the impurity such as remove dust enter rectifying tank 6, when refining Add refining auxiliary agent anhydrous K₂CO ₃(or Na₂CO ₃) and active carbon, anhydrous K₂CO ₃Or Na₂CO ₃Mainly Be dehydration, active carbon is the absorption high-boiling components, and heating-up temperature is 180～200 ℃, and vacuum is 0.07～0.09Mpa obtains the refining furfuryl alcohol finished product 7 of purity higher (can reach more than 98%). Be guaranteeing that safety, crude furfuryl alcohol enter on the pipeline of rectifying tank is provided with spark arrester.

The residue 8 behind the furfuryl alcohol is reclaimed in destructive distillation, through natural air high temperature oxidation process, heating-up temperature Be 250 ℃～300 ℃, be added to after the oxidation in the leaching groove 9, add simultaneously dilute sulfuric acid (15%) Or rare nitric acid (30%) solution leaches, and its leaching liquid enters in the lautertuns 10, isolates Filter residue 16, filtrate enter concentration tank 11, through heating evaporation, put into after being concentrated into finite concentration In the stirred crystallization groove 12, through the cooling and stirring crystallization, isolate mother liquor 13, it is returned concentrated In the tank 11, crystal is then put into centrifuge 14, and centrifugation obtains copper sulphate or copper nitrate.

Isolated filter residue 16 after the mantoquita leaching liquid filters mainly is chrome green, and helps Solvent 17 is added in the lump such as NaoH and carries out roasting in the roaster 18, sintering temperature 900 ℃ with On, make the generation sodium chromate, to pulverize after the roasting and put into leaching groove 19, water is at stirring condition Under leach, leaching liquid is through filter 21 elimination impurity, filtrate enters concentration tank 23, earlier Make solution be acid with sulfuric acid or acetic acid, be controlled at 5.5 such as pH value, heating concentrates, in stirring Mix cooling and stirring in the crystallization tank 24, isolate sodium sulphate or the sodium acetate of first crystallization, mother liquor continues Continuous crystallization, crystal is added to suction filtration in the filter 26, obtains the finished product sodium dichromate, as producing Potassium bichromate need to add potassium chloride after filtrate adds sulfuric acid or acetic acid, through concentrated, crystallization Isolate sodium chloride or sodium acetate, solution continues crystallization, obtains potassium bichromate through suction filtration.

Isolate filter residue 16 (being mainly chrome green) after the mantoquita leaching liquid filters and also can in oxidation furnace 29, pass into O₂Be higher than under 900 ℃ the high temperature as 1000 ℃ burning-off carbide and its His impurity obtains refining chrome green, and purity is more than 97%.

Because dead catalyst is paste raw materials, the present invention has adopted the institute such as Fig. 2 in the destructive distillation tank The agitator that shows, the structural representation of destructive distillation tank belt stirrer shown in Figure 2 is (on the destructive distillation tank Charge door, steam discharging opening not shown), be to adapt to the motion state of material, Electric Machine Control Device 34 and motor 35 adopt the operation of two-stage rotating speed, are respectively 25 rev/mins and 12 rev/mins; Stir Mixing slurry 32,39 is 90 ° of configurations; Stuffing box 37 is taked water cooling for adapting to the hot operation condition Mode; Explosion stack 33 doubles as explosion-proof and entrance oxidation air; For making blowing convenient, adopt Compound baiting valve 31 and be 30 ° of configurations, be conduction oil in the chuck 40.

The present invention is by the mode of destructive distillation, make the furfuryl alcohol in the dead catalyst obtain reclaiming, and can further obtain elaboration, purity is more than 98%, by making residue, improved the extraction mantoquita, the product quality of bichromate through high-temperature oxydation, when extracting bichromate, coproduction sodium sulphate or sodium chloride or sodium acetate.By technology of the present invention, make discarded catalyst obtain comprehensive utilization, created higher economic value, no waste residue is discharged products such as the furfuryl alcohol that can obtain meeting industrial standard, copper sulphate, copper nitrate, sodium dichromate, potassium bichromate, sodium sulphate, sodium acetate, chrome green.Adopted conventional equipment, process economics is feasible.

Embodiment one:

Discarded catalyst 400kg and 120kg water one furfuryl alcohol solvent (water content is 80～90%) pulp add the destructive distillation jar, and the conduction oil temperature is 180 ℃, 12 hours destructive distillation time, 1 hour residue natural air high-temperature oxydation time, get slightly pure 200kg, residue 140kg.

Embodiment two:

Discarded catalyst 320kg, aqueous solvent one furfuryl alcohol 100kg, 220 ℃ of conduction oil temperature, 0.8 hour residue natural air high-temperature oxydation time, get slightly pure 160kg, residue 140kg at 8 hours destructive distillation time.

Embodiment three:

Discarded catalyst 280kg, aqueous solvent one furfuryl alcohol 80kg, 250 ℃ of conduction oil temperature, 0.5 hour residue natural air high-temperature oxydation time, get slightly pure 150kg, residue 90kg at 6 hours destructive distillation time.

By above-mentioned three embodiment as can be seen, reinforced suitably minimizing, heating-up temperature suitably improves, and yield can improve, and the production cycle also can shorten.Therefore, select for use during destructive distillation of the present invention heating-up temperature be 250 ℃～350 ℃ comparatively suitable, vacuum is 0.07～0.09MPa.

Claims

1, the method for comprehensive utilization of dead catalyst is characterized in that dead catalyst is carried out destructive distillation during the fluid bed furfuryl alcohol was produced, and reclaimed the crude product furfuryl alcohol, and the destructive distillation condition is that under agitation heating-up temperature is 250～350 ℃, and vacuum is 0.07～0.09MPa.

2, method according to claim 1 is characterized in that the preceding dead catalyst of destructive distillation adopts lower boiling water-furfuryl alcohol solvent to dilute.

3, method according to claim 1 is characterized in that the crude product furfuryl alcohol that reclaims carries out rectifying, obtains refining furfuryl alcohol.

4, method according to claim 3 adds auxiliary agent potash or sodium carbonate and active carbon when it is characterized in that rectifying.

5, method according to claim 1 is characterized in that reclaiming residue behind the crude product furfuryl alcohol 250～300 ℃ of following oxidations, and mantoquita is extracted in the back.

6, method according to claim 5, it is characterized in that described residue oxidation after, with dilute sulfuric acid or rare nitrate leaching, produce copper sulphate or copper nitrate.

7, method according to claim 6 is characterized in that the filter residue after described leaching liquid filters is Cr ₂O ₃,, produce bichromate after the roasting with cosolvent NaOH roasting.

8, method according to claim 7 is characterized in that Cr ₂O ₃With the NaOH roasting after pulverize and use water extraction, the leaching liquid filtration, filtrate is used H ₂SO ₄Or HAc makes solution be acid, and the back concentrates, Crystallization Separation goes out Na ₂SO ₄Or NaAc, filtrate is continued crystallization, makes the sodium dichromate crystal.

9, method according to claim 8 is characterized in that described filtrate adds H ₂SO ₄Or add KCl behind the HAc again, and isolate NaCl or NaAc crystal, filtrate is continued crystallization, makes potassium bichromate.

10, method according to claim 6 is characterized in that the filter residue after described leaching liquid filters is Cr ₂O ₃Aerating oxygen is being higher than 900 ℃ of following high-temperature oxydations, obtains refining chrome green.