CN1003183B

CN1003183B - Method for enhancing burning of fire bed furnace

Info

Publication number: CN1003183B
Application number: CN85102001A
Authority: CN
Inventors: 宋鸿升
Original assignee: Individual
Current assignee: Individual
Priority date: 1985-04-04
Filing date: 1985-04-04
Publication date: 1989-02-01
Also published as: CN85102001A

Abstract

The present invention belongs to the technical field of the reform of solid fuel layer combustion, which relates to a furnace which changes the existing single layer combustion into two strengthening combustion centers of hearth layer combustion and advanced chamber combustion to increase the efficiency and the intensity of the chamber combustion, promote the combustion rate of the layer combustion and achieve the purposes of saving energy, eliminating smoke and increasing heat efficiency. In the selected proper partial space of a furnace chamber, a plurality of spatial cross sections basically vertical to layer combustion furnace gas entering the space are selected. A plurality of air nozzles are arranged on the proper positions of the furnace wall of each cross section, and a plurality of gas jet streams are jetted by each air nozzle along the tangential direction of a plurality of spatial imaginary concentric circles from axle centers to the furnace wall in the cross sections. After the jet streams carry out various kinds of exchange with furnace gas and carbon particles entering a combustion chamber, a spiral turbulence combustion chamber in an advanced powder structure is formed.

Description

The intensifying combustion mothod of grate stove

The invention relates to processing method based on the strongly acidic cation exchange catalysts of styrene/divinyl benzene copolymer.

Recently in organic chemistry, often used cation exchange catalysts as the synthetic instrument useful of acid-catalysis to ecology.Relating to synthetic example has esterification, the cracking of ester, hydrolysis, condensation, hydration and aromatic alkylation and acetylation.They are that catalyst is separated from product easily than the superior part of liquid acids, and unlike traditional homogeneous catalysis spent acid are arranged.

It is that enough selectivity and space/time productive rate not only will be arranged that solid-state cation exchange thing can replace liquid acids to make the actual prerequisite of using, and copolymer will have heat endurance under various reaction conditions.

Core is good by strongly acidic styrene/divinyl benzene copolymer heat endurance spy that halogen has replaced, and it is synthetic to can be used for 100 to 200 ℃ of acid-catalysis in the temperature range, for example in the hydration or alkylated reaction of low alkene.

In british patent specification 1393594, described its core and replaced the production method of cation-exchanger once at least by halogen, and pointed out to be used for the situation of water and the various reactions of anhydrous medium under 100 to 200 ℃ of temperature as thermally stable catalyst.

The strongly acidic cation exchanger of core-chlorination and core-fluoridize was compelling especially catalyst in recent years.

But produce to need with the fragrant monomer of core-halogenation for example chlorostyrene or fluorostyrene can't buy on market or cost an arm and a leg.

US Patent specification 3,256,250 and 4,269,943 core-halogenation has been described the manufacture method of strongly acidic cation exchanger.First piece of patent specification is the at first sulfonation of styrene/divinyl benzene copolymer, core-chlorination or core-fluoridize then, and second piece of patent specification is first core monochlor(in)ate or core-bromination, sulfonation then.

The core one halogenation strongly acidic cation exchanger that uses produced in several ways is during as catalyst, has hydrogen halides and sulfuric acid comes off in initial 200 to 300 hours.For example when becoming corresponding pure time-like to low alkene hydration, usually when the petrohol and the tert-butyl alcohol, have a large amount of chlorine and sulfonic acid group from chlorated catalyst and split away off with the pattern of hydrochloric acid and sulfuric acid with 3 to 5 carbon atoms.Having observed them already has the deep-etching effect to stainless steel reactor, the erosion of depression points and minute crack occurs, causes inside reactor and wadding all destroyed.Simultaneously, such catalyst can be lost 50% activity, and the catalyst matrix of part can be destroyed.

Therefore, the purpose of this invention is to provide a feasible method, make with styrene/divinyl benzene copolymer be base, its core by halogenation strongly acidic cation exchange catalysts, permission is used in stainless steel reactor, and substantially can be not destroyed or this energy of rupture is remained within the limit of permission.

The present invention addresses this problem like this, and promptly the strongly acidic cation exchanger that core has been replaced by halogen is being used as before catalyst uses, and carries out preliminary treatment with deionized water under the situation of high temperature and no oxonium ion, metal ion earlier.

Preliminary treatment preferably is warmed up to 155 ℃ and have under the condition that pressure exists then by 110 ℃, makes it to handle under liquid phase.

Preliminary treatment is finished in its surface and the contacted device of strongly acidic cation exchanger usually, and does not contain iron in the treatment fluid, for example finishes in the device of making lining with enamel, glass, pottery, tetrafluoroethene or other heat-staple plastics.

Re-use after preferably the oxygen that dissolves in the water being removed half.

Desirable embodiment is to finish preliminary treatment with one or more alcoholic solutions of 1 to 4 carbon atom, suitable especially is to adopt the deionized water solution that contains 3 to 4 carbon atom alcohols, concentration generally is the alcohol that contains 0.5% to 20% volume, and the best is the alcohol of 1% to 10% volume.

Preliminary treatment must proceed to the H that exfoliation rates is less than 25 milligrams ₂SO ₄/ rise catalyst * hour and 7 milligrams HCl/ rise catalyst * hour till.

Have been found that with demineralized water 100 to 150 ℃ adding depress in rustless steel container, wash core-chlorated catalyst after, the mechanical stability of catalyst has degenerated.This is because the depolymerization of catalyst has partly completely lost due to its stability.

But,, depress in enamelled vessel washing after about 400 hours, chlorine and sulfonic acid group (SO adding if be raised to 155 ℃ in temperature then by 110 ℃ with demineralized water ^- ₃) falling speed just very low, thereby the strongly acidic cation exchanger of core-chlorination just can be used as catalyst without a doubt, for example can be used for making the low alkene of 3 to 5 carbon atoms to play aquation.And generate corresponding alcohols.But when the organic sulfonic acid of high level (about 50 mg/litre water) was arranged in the washings, then the long-time stability of catalyst can descend.

Be surprisingly found out that,, particularly use C when preliminary treatment is with the demineralized water of anaerobic and non-metallic ion ₃Or C ₄When the solution of alcohol in deionized water was finished, with sulfonation after styrene/divinyl matrix elder generation halogenation, or the thermo mechanical stability of the strongly acidic cation exchanger of reversed sequence manufacturing can keep more than 8,000 hours fully.With with demineralized water by comparison.With 0.5-20% the best is the C of 1-10% ₃Or C ₄Alcohol solution can reduce by 50% processing time.In the alcoholic solution that substep is discharged, every liter only detects and is lower than 2 milligrams oligomeric sulfonic acid fragment.

The strongly acidic cation exchanger of core-halogenation of handling like this can be in stainless steel reactor commonly used, not only can carry out propylene direct hydration and become isopropyl alcohol but also positive ethylene hydration can be become sec-butyl alcohol and do not have etching problem and produce when temperature is higher than 150 ℃.And activity of such catalysts almost remained unchanged in thousands of hours.

Described a strongly acidic cation exchanger among Fig. 1 and carried out pretreated optimum implementation core-halogenation.Wherein demineralized water or alcoholic solution are added in the auto levelizer 2, get rid of, solution is transported in the container handling 5 by pipeline 4 with pump 3 then with the oxygen that nitrogen will be dissolved in the device 2 by pipeline 1.In container handling 5, both can feed water or alcohol solution at every turn, and, use to make 80% to 90% solution circulation by pipeline 7 and 4, from circulate, only discharge step by step as waste water to 20% 10% with pipeline 8 with pipeline 8 blowings.This cyclic process is favourable, especially for industrial production, otherwise can consume demineralized water or alcoholic solution in a large number.

Following each example is that explanation is of the present invention.Performance for the pretreated catalyst of experimental evidence the present invention, according to the example in the German patent specification 2,233,967 9 catalyst is used for producing sec-butyl alcohol (subA) according to the example in the German patent specification 2,429,770 2 from n-butene from the production of propylene manufacturing isopropyl alcohol (IPA).

Comparison example

The container handling that is illustrated among Fig. 1 is with long 3.0 meters, the 1.4571(316SS that diameter is 26 millimeters) the stainless steel formation.This stainless steel tube is added with vapour jacket.In order to adjust temperature.All are taken over and pump 3 all uses not same material (316SS) to make.The cation-exchanger that will contain 3.7 milliequivalents sulfonic acid/gram dry and 5.5 milliequivalents chlorine/gram material is incorporated in the pretreatment unit according to Fig. 1 for 1,000 milliliter.

By pipeline 1 with 1 liter/time charging rate in the groove of stainless steel tube, pump into the demineralized water that still contains some residual oxygen.With Steam Heating temperature is adjusted to 155 ℃.Because Cl ^-And SO ₃H ^-The hydrolysis of group comes off and the current that contain hydrochloric acid and sulfuric acid are to release from the head that the pipe internal pressure maintains the stainless steel tubes of 10 crust, these current 20 ℃ of coolings down.Check the generating rate of hydrochloric acid and sulfuric acid with chemical analysis.The milligram numerical value (milligram/catalyst liter * hour) of later every liter of catalyst hour was listed in and showed in the I each hour.

The table I

Hour milligram H ₂SO ₄Milligram HCl milligram organic sulfonic acid

Afterwards catalyst liter * hour catalyst liter * hour catalyst liter * hour

4 190 1，030 1，350

24 60 175 850

72 45 80 800

120 35 29 580

240 29 12 550

360 21 6 530

After catalyst was shifted out from pretreatment unit, it was brown transparent to find to have approximately 20% catalyst to become, similar in appearance to the thing of frog's egg.Not destruction to catalyst is partly measured, and finds to also have 28% residual capacity.Yet still the mechanical stability of unbroken catalyst member is to have weakened greatly.When this catalyst being used for the synthetic IPA of propylene direct hydration, have to 50% theoretical efficiency.

Embodiment

Begin to be warmed up to 155 ℃ then and finish processing containing the 1%subA same solution at 110 ℃.And in order to reduce the generation of the aqueous solution, the solution with 90% recycles, and the solution that substep is discharged has only 10%.Obtain following exfoliation rates:

The table II

Hour milligram H ₂SO ₄Milligram HCl milligram organic sulfonic acid temperature

Afterwards catalyst liter * hour catalyst liter * hour catalyst liter * hour ℃

4 54 302 1.5 110

24 35 95 1.1 120

72 38 71 1.2 148

100 37 62 1.4 155

120 34 40 1.4 155

160 29 17 1.2 155

200 22 9 1.0 155

210 21 6 1.1 155

From corresponding alkene direct hydration petrohol and sec-butyl alcohol process, the various characteristics of the catalyst of handling like this can be compared U.S. with the catalyst that obtains in example 3 and the example 4 with active.

Because temperature program(me) has reduced the total losses of sulfonic acid, in direct hydration reaction synthol or alkylation were synthetic, life of catalyst was longer.

Claims

1, a kind of processing is the method for the strongly acidic cation exchange catalysts of base with styrene/divinyl benzene copolymer, it is characterized in that, the strongly acidic cation exchanger that core has been replaced by halogen is as before the catalyst, in a pretreatment unit, spend except the deionized water of dissolved oxygen and finish preliminary treatment, wherein pretreatment unit with the equal iron content not of the contacted material of strongly acidic cation exchange catalysts and treatment fluid, there are not aerobic and iron during processing yet, temperature when carrying out described the processing rises to 155 ℃ gradually by 110 ℃, pressure is for allow handling the pressure that carries out under liquid phase, and this preliminary treatment is proceeded to falling speed is less than 25 mm H ₂SO ₄/ catalyst liter * hour and be less than 7 milligrams of HCI/ catalyst liters * hour till.

2, method according to claim 1 is characterized in that, described processing is to be the 0.5-20%(volume at alcohol that contains 1-4 carbon atom of one or more tools and content) described deionized water in carry out.