EP2558550A2

EP2558550A2 - Method for thermally cleaving organic waste having high molecular weight

Info

Publication number: EP2558550A2
Application number: EP11719755A
Authority: EP
Inventors: Thomas Willner
Original assignee: Nexxoil AG
Current assignee: Nexxoil AG
Priority date: 2010-04-13
Filing date: 2011-03-03
Publication date: 2013-02-20
Also published as: US8858656B2; IL222416A0; CN103038317B; AU2011240449A1; WO2011127881A3; US20130091761A1; CN103038317A; IL222416A; CA2814880C; WO2011127881A2; DE102010014768B4; AU2011240449B2; BR112012026395B1; CA2814880A1; DE102010014768A1

Abstract

The invention relates to a method for thermochemically converting organic waste material having high molecular weight into liquid combustible materials and fuels, comprising the following steps: feeding organic waste material into a reactor, heating the organic waste material to a temperature between 250 °C and 500 °C while avoiding exceeding critical coking temperatures in the reactor, feeding biogenic substances to the reactor, collecting and condensing the gases and vapors released from the mixture of organic waste material and biogenic substances, collecting the condensate and letting phases form, and removing the phase(s) containing liquid combustible materials and fuels.

Description

Process for the thermal decomposition of high molecular weight organic waste

The invention relates to a process for the thermochemical conversion of

high molecular weight organic waste material in liquid fuels.

By high molecular weight organic waste material here are solid hydrocarbon-containing substances or mixtures of long-chain or crosslinked molecules to understand. Such waste materials may, for. As plastic or rubber waste,

Distillation residues from mineral oil processing, heavy oils of all kinds, asphalts, bitumen, tar sands or oil shale.

The Conventional Process for the Catalytic Cracking of High Molecular Weight

Hydrocarbons in mineral oil processing is the so-called FCC process (fluid catalytic cracking). Here, the reaction is in a circulating

Gas fluidized bed performed. The fluidized catalyst migrates back and forth between the cracking reactor operating at about 500 ° C and the regenerator operating at about 700 ° C. In the FCC process, the reactant in the reactor must be completely vaporized before the cracking reactions can take place on the fluidized catalyst particles. This is not possible with high-molecular weight hard-to-evaporate solids such as plastic, tar sands or oil shale.

Performing the cracking reactions at lower temperatures below 500 ° C, the high molecular weight starting materials are no longer completely evaporated, so that they are predominantly in the liquid phase. However, because of the lower

Temperatures used to accelerate the reaction rate very active catalysts. A crucial problem with the use of cracking catalysts such as zeolites in liquid phase reactions, however, is that they lose their activity very rapidly, in particular due to charring reactions. This leads to high operating costs.

CONFIRMATION COPY DE 102 15 679 B4 describes the thermal conversion of high molecular weight substances into liquid fuels, in which the cracking reactions take place in a heavy oil liquid phase, a so-called sump phase, in a temperature range between 350 and 500 ° C. Here, the autocatalytic action of the heavy oil fraction is used by using a gas stream which has a hydrogenating or reducing effect. However, the use of hydrogenating or reducing gas requires increased

Operating pressures of usually more than 5 MPa. In addition, in the application of DE 102 15 679 B4 it should be noted that the reaction temperatures must be sufficiently low so that the containers, pipes and heating elements do not coke. With critical coking temperatures one must expect material-dependent above 400 to 450 ° C. In order to avoid coking, the reaction temperatures must be below the respective critical coking temperature, in particular on heated walls. For temperature-stable hydrocarbons such as plastic and rubber waste, distillation residues from mineral oil processing, tar sands or oil shale higher reaction temperatures are necessary according to the method of DE 102 15 679 B4, so that for these hydrocarbons coking strongly affect the technical implementation. Another disadvantage of DE 102 15 679 B4 is the need for very rapid heating of the raw material. As a result, there are excessive

Wall temperatures that lead to coking, usually unavoidable.

The need for excessive reaction temperatures in the mentioned

Hydrocarbons are also particularly applicable to pyrolysis processes, ie purely thermal decomposition, so that even there unwanted coking reactions represent a significant procedural problem.

In DE 19742266 AI a method is described in which plastic can be converted together with biomass in crude oils: In this method, water is used as an aid (hydrolytic cleavage). Therefore, due to the process, very high pressures of about 20 MPa are necessary. There is therefore a need for a method for cleaving said

Hydrocarbons, which runs under atmospheric pressure, does not require the addition of catalysts and can be carried out at reaction temperatures below critical coking temperatures, where it also covers the non-evaporable

Components can convert high molecular weight organic waste material into liquid fuels.

The object is achieved by the method mentioned in claim. The subclaims reflect advantageous embodiments of the invention.

The method according to the invention comprises the following steps:

• Heating the high molecular weight organic waste material to temperatures

between 250 ° C and 500 ° C, preferably between 280 ° C and 420 ° C, more preferably between 300 ° C and 400 ° C, while avoiding exceeding critical coking temperatures in a reactor or alternatively in one

Preheater with subsequent transfer to a reactor

• Addition of biogenic substances

• cooling the released gas-vapor phase, condensing the vapor components and

Collecting the formed condensate phases

• Separation and separation of the formed phases

The individual steps of the method according to the invention do not necessarily have to be carried out successively. It is possible to deviate from these steps

Run sequentially or in particular in a continuous operation simultaneously.

The high-molecular organic waste material and the biogenic substances are to be supplied in a crushed state. Alternatively, the waste material, if fusible, may be processed in a molten state. It has proven advantageous to stir during the transformation or otherwise to keep the material in motion. Other measures include, for example, inert fluidizing gases when the materials are in the reactor as a solid mixture, or circulation pumps when the waste material in the reactor is in a molten flowable state.

It was surprisingly found that high molecular weight organic

Waste material at atmospheric pressure without the addition of catalysts

Temperatures of up to 500 ° C, but below the coking temperatures, ie usually below 400 ° C, under detection of the non-volatile components in liquid fuels can convert when biogenic substances are supplied. Often even unexpectedly low reaction temperatures of less than 350 ° C are found where most high molecular weight organic waste materials would not decompose without the addition of biogenic material.

In this context, biogenic substances are understood to mean substances whose origin in the

Is essentially biological. For example, all materials containing carbohydrates such as cellulose, starch and sugar, for example straw, miscanthus, maize, green waste, wood etc., as well as contaminated wood, as well as all materials containing proteins, for example dried sewage sludge, port silt, are suitable , Animal meal, etc. Overall, therefore, basically almost all plant and animal materials and their processing products such as paper, cardboard, food residues or leather are suitable. Surprisingly, the biogenic substances may even be contaminated, for example by heavy metals, sulfur or halogens.

It surprisingly turns out that the condensed hydrocarbon liquid product oils usable as liquid fuels and fuels are virtually free of interfering biogenic decomposition products. In the case of contamination as described above, the product oils surprisingly remain free or nearly free of them

Contamination.

As high molecular weight organic waste material, substances containing long-chain and / or branched hydrocarbon molecules, such as, for example Plastic or rubber waste, distillate residues from mineral oil processing, heavy oils of all kinds, asphalts, bitumen, tar sands or oil shale.

The inventive method is explained in more detail by the flowchart in Fig. 1.

The high molecular weight organic waste material is brought to temperatures of 250 ° C to 500 ° C, preferably from temperatures between 280 ° C and 420 ° C, more preferably between 300 ° C and 400 ° C. This can be done in a reactor or in one

Preheater with subsequent transfer to a reactor. For this purpose, heaters of many types such as electric heating - for example, via resistance, induction or high frequency -, burner exhaust systems or many others can be used.

After addition of biogenic substances according to the invention, the high molecular weight organic waste materials begin to break down into shorter-chain liquid fuels in the light and medium oil range.

These evaporate in the reactor and are passed through the gas-vapor phase from the top of the reactor and then re-liquefied their vapor components by cooling and condensation.

Contrary to expectations, the recovered condensed hydrocarbon liquid product oils remain virtually free of interfering biogenic decomposition products.

The biogenic substances themselves undergo pyrolytic decomposition reactions. As a rule, the resulting biogenic pyrolysis products during the reaction are first of all a solid residue which is discharged directly from the reactor and does not enter the gas-vapor phase, secondly leaving gases which do not condense and, thirdly, biogenic condensation phases. The same applies to the above-mentioned contamination of the biogenic substances. This results in several immiscible condensate phases, which are arranged separately in the condensate by density on top of each other and can be mechanically separated from each other in a simple manner. This simple separation of the product phases is particularly advantageous.

A particular advantage of the process according to the invention is the fact that it is also possible to process here non-completely volatilizable high molecular weight organic residues which are solid at room temperature.

The special features of the method according to the invention are:

• The process is under atmospheric pressure.

• In the process, a temperature of 400 ° C is usually not exceeded.

• No catalysts are needed.

• There are no other reaction auxiliaries, such as As water or gases necessary.

• The resulting product condensate phases can be easily achieved

mechanically separate from each other.

The process of the invention can be carried out in batch mode or continuously.

The invention will be explained in more detail with reference to the following example: There are as high molecular weight hydrocarbon 8 kg of a

Vacuum distillation residue from mineral oil processing, which is solid at room temperature, presented in a laboratory stirred reactor.

By means of electrical jacket heating on the reactor, this feedstock is heated to 390 ° C. Subsequently, as a biogenic substance dried and crushed straw by means of a screw conveyor continuously with constant stirring the reactor

fed. During the straw intake, the formation and release of

observed evaporating fission products on the gas-vapor phase, which is continuously discharged from the top of the reactor and passed through a cooling condenser. The condensate is collected continuously in a separating funnel.

The non-condensing gas phase is removed via a fume hood. By doing

Separating funnels become four superimposable immiscible liquid phases

collected. After ascending density from top to bottom, there are firstly a dark brown oil phase (condensate phase 1), secondly a blackish-brown organic phase (condensate phase 2), third a reddish brown aqueous phase (condensate phase 3) and fourthly a black-brown organic phase (condensate phase 4).

In total, 2 kg of straw are supplied over 2 hours. At the end of the experiment 4.21 kg of residue are taken from the reactor. An extractive analysis shows that this residue consists of 0.72 kg char residue and 3.49 kg heavy oil residue. 4.14 kg of phase 1, 0.24 kg of phase 2, 0.58 kg of phase 3 and 0.09 kg of phase 4 are collected in the condensate. The balance difference is 0.74 kg of gas.

According to a gas analysis, this noncondensing gas consists of about half of oxygen-containing fission products such as carbon dioxide and carbon monoxide and the other half of hydrocarbon fission products such as methane, ethane, propane and butane. Also their olefins ethylene, propylene and butylene were found.

In Fig. 2 is a GC-MS analysis of the condensate phase 1, the inventive

Product oils, in addition to tabular evaluation of the signals shown. It can be seen that predominantly saturated unbranched alkanes have been formed, with the associated, usually smaller, olefin peak being recognizable almost immediately adjacent to each alkane peak. Disturbing biogenic fission products such. B. Phenol derivatives are virtually impossible to find.

For GC-MS analysis, a device from Agilent type HP5972A is used, as separation column was a cyanopropylphenol and polysiloxane coated type ZB1701 from Zebron used. The heating rate is (3 ° C / min). The

Temperature program covers the range from 45 ° C to 280 ° C. Fluoranthene (retention time 70.05 min) was used as the internal standard. To demonstrate the freedom of biogenic residues in the hydrocarbon product oil (Phase 1), a C14 isotope analysis was performed. This resulted in a biogenic C content in the product oil of less than 5%.

The aqueous phase (condensate phase 3) contains acetic acid as well as water

Main component. In addition, there are other water-soluble oxygenated organic components such. As formic acid, aldehydes, ketones, alcohols and acetates to find.

The other two organic condensate phases, Phase 2 and Phase 4, consist predominantly of oxygen-containing ring compounds such. B. phenol derivatives. Pure paraffinic hydrocarbons such. B. n-alkanes are not found there.

Claims

1. A process for the thermochemical conversion of high molecular weight organic waste material into liquid fuels, comprising the steps of:

Feeding organic waste material into a reactor,

- Heating the organic waste material to a temperature between 250 ° C and 500 ° C while avoiding exceeding critical

Coking temperatures in the reactor,

Feeds of biogenic substances to the reactor,

- collecting and condensing the mixture of organic

Waste material and biogenic substances liberated gases and vapors,

Collecting the condensate and forming phases,

- Remove the liquid fuel and fuel phase or

Phases.

2. The method according to claim 1, characterized in that the organic

Waste material consists of long-chain and / or branched hydrocarbon molecules.

3. The method according to any one of the preceding claims, characterized in that the organic waste material from plastic or rubber waste,

Distillation residues from mineral oil processing, heavy oils, asphaltene, bitumen, tar sands and / or oil shale.

4. The method according to any one of the preceding claims, characterized in that the biogenic material of plant and / or animal origin.

5. The method according to any one of the preceding claims, characterized in that the biogenic material cellulose, starch, sugar, straw, miscanthus, corn, green waste, wood, proteins, sewage sludge, harbor silt, meat and bone meal, paper, cardboard,

Food residues and / or leather is.

6. The method according to any one of the preceding claims, characterized in that the organic waste material is tempered before feeding.

7. The method according to any one of the preceding claims, characterized in that the method is carried out under atmospheric pressure.

8. The method according to any one of the preceding claims, characterized in that the temperature in the reactor is between 280 ° C and 420 ° C.

9. The method according to any one of the preceding claims, characterized in that the temperature in the reactor is between 300 ° C and 400 ° C.

10. The method according to any one of the preceding claims, characterized in that the weight ratio of organic waste material to biogenic substances is 4: 1.